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EP4374433A2 - Lithium-schwefel-batteriekathode aus mehreren kohlenstoffhaltigen regionen - Google Patents

Lithium-schwefel-batteriekathode aus mehreren kohlenstoffhaltigen regionen

Info

Publication number
EP4374433A2
EP4374433A2 EP22822712.0A EP22822712A EP4374433A2 EP 4374433 A2 EP4374433 A2 EP 4374433A2 EP 22822712 A EP22822712 A EP 22822712A EP 4374433 A2 EP4374433 A2 EP 4374433A2
Authority
EP
European Patent Office
Prior art keywords
battery
anode
cathode
lithium
zone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22822712.0A
Other languages
English (en)
French (fr)
Inventor
Bruce Lanning
Michael W. Stowell
Anurag Kumar
Jeffrey Bell
Qianwen Huang
Jesse Baucom
You Li
John Thorne
Karel Vanheusden
Elena Rogojina
Jerzy Gazda
Jingning Shan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lyten Inc
Original Assignee
Lyten Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US17/383,744 external-priority patent/US11342561B2/en
Priority claimed from US17/383,756 external-priority patent/US12126024B2/en
Priority claimed from US17/383,735 external-priority patent/US11489161B2/en
Priority claimed from US17/383,803 external-priority patent/US11309545B2/en
Priority claimed from US17/383,793 external-priority patent/US11398622B2/en
Priority claimed from US17/383,769 external-priority patent/US20210359308A1/en
Priority claimed from US17/563,183 external-priority patent/US11404692B1/en
Application filed by Lyten Inc filed Critical Lyten Inc
Publication of EP4374433A2 publication Critical patent/EP4374433A2/de
Pending legal-status Critical Current

Links

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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

  • This disclosure relates generally to batteries, and, more particularly, to lithium-ion batteries that can compensate for operational cycle losses.
  • composition of matter including a plurality of pores.
  • the composition of matter which may be suitable for incorporation into a battery electrode, includes a plurality of particles, each of the particles containing a first zone including a plurality of first pores having a uniform pore size and a second zone including a plurality of second pores.
  • the second zone may be concentrically positioned relative to the first zone and separated from the first zone by at least some of the plurality of first pores, where the plurality of second pores has a pore size that gradually decreases along a radial direction from the center of the particle to a boundary of the particle.
  • the composition of matter may also include a plurality of aggregates, each including a multitude of the particles joined together, and a plurality of agglomerates, each including a multitude of the aggregates joined together.
  • each of the particles may have a principal dimension in between 20 nanometers (nm) and 150 nm.
  • Each of the aggregates may have a principal dimension in between 10 nanometers (nm) and 10 micrometers (pm).
  • Each of the agglomerates may have a principal dimension in between 0.1 pm and 1,000 pm.
  • At least some of the pores may be dispersed throughout one or more of the particles or the aggregates, where each of the pores may have a principal dimension in between 0 nm and 100 nm.
  • each of the particles may include a first porosity region and a second porosity region that is positioned adjacent to the first porosity region.
  • the first porosity region may have a first type of pores and the second porosity region may have a second type of pores, such that the first porosity region has a different porosity than the second porosity region.
  • the first type of pores may have a first pore density
  • the second type of pores have a second pore density.
  • the first porosity region may have a first pore density between 0.0 cubic centimeters (cc)/g and 2.0 cc/g
  • the second porosity region may have a second pore density between 1.5 and 5.0 cc/g.
  • the second porosity region may be at least partially encapsulated by the first porosity region.
  • the pores may be interspersed throughout the agglomerates, where at least some of the pores have a principal dimension in between 1.3 nm and 32.3 nm. Electrically conductive additives may be dispersed within at least some of the pores.
  • the composition of matter may have exposed carbon surfaces with a surface area in between 10 m 2 /g to 3,000 m 2 /g and/or a composite surface area (e.g., with sulfur micro-confined within the pores) in between 10 m 2 /g to 3,000 m 2 /g.
  • the composition of matter may have an electrical conductivity in between 100 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi).
  • the particles, aggregates, and/or agglomerates may include exposed carbon surfaces that may assist in the nucleation of sulfur, such that the composition of matter has a sulfur to carbon weight ratio between approximately 1:5 to 10:1.
  • some of the agglomerates are connected to each other with one or more polymer-based binders.
  • the battery may include an anode, a polymeric network disposed over one or more exposed surfaces of the anode, a cathode positioned opposite to the anode, an electrolyte at least partially dispersed throughout the cathode and in contact with the anode, the electrolyte configured to transport the plurality of alkali ions between the cathode and the anode, and a separator.
  • the anode may include an alkali metal that can release alkali ions during operational discharge- charge cycling of the battery.
  • the polymeric network may include carbonaceous materials grafted with fluorinated polymer chains cross-linked with each other.
  • the fluorinated polymer chains may produce an alkali-metal containing fluoride in response to operational cycling of the battery.
  • formation of the alkali-metal containing fluoride may suppress alkali metal dendrite formation from the anode, for example, such that lithium is consumed to form lithium fluoride rather than forming lithium-containing dendritic structures.
  • the electrolyte may be at least partially dispersed throughout the cathode and in contact with the anode and may assist in the transport of the alkali ions between the cathode and the anode.
  • the separator may be positioned between the anode and the cathode.
  • the carbonaceous materials may include flat graphene, wrinkled graphene, carbon nano-tubes (CNTs), and/or carbon nano-onions (CNOs).
  • the fluorinated polymer chains may include monomers including 2, 2, 3, 3, 4, 4, 5, 5, 6, 6,7,7- Dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate (OFPMA), Tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-Trifluoro-2- hydroxy-2-(trifluoromethyl)propyl]bicyclo[2.2.1]hept-2-yl methacrylate (HFA monomer), and/or vinyl-based monomers including 2,3,4,5,6-Pentafluorostyren
  • the fluorinated polymer chains may be grafted to a surface of the carbonaceous materials, such that the grafting may be based on radical initiators including at least one of benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN).
  • BPO benzoyl peroxide
  • AIBN azobisisobutyronitrile
  • the fluorinated polymer chains may chemically react with alkali metal ions via a Wurtz reaction, which may be associated with production of the alkali metal fluoride.
  • Graphene nanoplatelets may be dispersed throughout the polymeric network, where the graphene nanoplatelets are isolated from each other within the polymeric network. The dispersion of the graphene nanoplatelets may include different concentration levels (of the graphene nanoplatelets).
  • the dispersion of the graphene nanoplatelets may include carbonaceous materials functionalized with at least some fluorinated polymer chains.
  • the polymeric network includes between approximately 0.001 wt.% to 2 wt.% of the fluorinated polymer chains.
  • the polymeric network includes an interphase layer in contact with the anode and a protective layer disposed on top of the interphase layer. The interphase layer may be based on a Wurtz reaction at an interface between the anode and the polymeric network.
  • the cross-linked polymeric network may include between approximately 5 wt.% to 100 wt.% of carbonaceous materials grafted with fluorinated polymer chains with a remaining balance of fluorinated polymers, non-fluorinated polymers, or cross-linkable monomers, or combinations thereof.
  • the carbonaceous materials grafted with fluorinated polymer chains may include 5 wt.% to 50 wt.% of fluorinated polymer chains and a balance of carbonaceous material.
  • the polymeric network may further define a density gradient associated with self-healing properties of the interphase layer and/or the protective layer and may strengthen the polymeric network, which may suppress dendritic growth from the anode.
  • the anode may be an alkali metal layer and/or include surfaces exposed to the electrolyte, where each exposed surface may include alkali metal-containing nanostructures or microstructures.
  • the alkali metal-containing nanostructures or microstructures may include carbonaceous particles, a number of aggregates each including carbonaceous particles, or a number of agglomerates each including several aggregates.
  • each of the carbonaceous particles has a first porosity region with a first pore density and a second porosity region with a second pore density.
  • the second porosity region may be at least partially encapsulated by the first porosity region, and the second density may be less than the first density.
  • the second porosity region may at least temporarily micro-confine an elemental sulfur as may be associated with operational discharge-charge cycling of the batter.
  • the anode may be structurally defined by a three- dimensional (3D) scaffold and/or stmcture, which may include adjacent graphene sheets that may at least intercalate alkali metal.
  • the anode may be formed as a lattice with adjacent graphene sheets that have exposed surfaces for alkali metal electrodeposition and/or intercalation.
  • a film may be disposed on the cathode and include a lattice with a tri-functional epoxy compound and a di-amine oligomer compound chemically bonded to each other. The film may bond with alkali metal containing poly sulfide intermediates generated during operational discharge-charge cycling of the battery and complement the polymeric sheath disposed on the anode.
  • a battery including an anode, a cathode positioned opposite to the anode, a protective sheath disposed on the cathode, an electrolyte, and a separator.
  • a polymeric network may be disposed on the anode and may include carbonaceous materials grafted with a plurality of fluorinated polymer chains cross-linked into a lattice.
  • the lattice may produce an alkali metal fluoride in response to operational cycling of the battery.
  • the alkali metal fluoride may be configured to suppress alkali metal dendrite formation from the anode.
  • the anode may output alkali ions during operational cycling of the battery.
  • the protective sheath disposed on the cathode may include a tri-functional epoxy compound and a di-amine oligomer-based compound, both of which may chemically react with each other.
  • the electrolyte may disperse throughout the cathode and contact with the anode.
  • the separator may be positioned between the anode and the cathode.
  • the polymeric network may be deposited over one or more exposed surfaces of the anode.
  • the carbonaceous materials may include one or more of flat graphene, wrinkled graphene, a plurality of carbon nano-tubes (CNTs), or a plurality of carbon nano-onions (CNOs).
  • the fluorinated polymer chains may include a plurality of monomers, one or more monomers including 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate (OFPMA), Tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-Trifluoro-2-hydroxy-2-
  • DFHA 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl acrylate
  • HDFDMA 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate
  • OFFPMA 2,2,3,3,4,4,5,5-Octa
  • the polymeric network may have a thickness approximately between 0.001 pm and 5 pm. Fluorinated polymer chains may be grafted to a surface of a respective one of the carbonaceous materials.
  • the fluorinated polymer chains may chemically interact with the one or more surfaces of the alkali metal of the anode via a Wurtz reaction.
  • the carbonaceous materials may include graphene nanoplatelets dispersed throughout the polymeric network.
  • the graphene nanoplatelets may be isolated from each other within the polymeric network.
  • the dispersion of the plurality of graphene nanoplatelets throughout the polymeric network may have different concentration levels.
  • the graphene nanoplatelets may be functionalized with the fluorinated polymer chains.
  • the polymeric network includes between approximately 0.001 wt.% to 2 wt.% of the fluorinated polymer chains.
  • the polymeric network may include an interphase region in contact with the anode and a protective region disposed on top of the interphase region.
  • the interphase region may be based on a Wurtz reaction at an interface between the anode and the polymeric network.
  • the interphase region may include one or more of a plurality of cross-linkable monomers including methacrylate (MA), acrylate, vinyl functional groups, or a combination of epoxy and amine functional groups.
  • the protective region may be characterized by a density gradient, which may be associated with self-healing properties of the protective region. The density gradient may strengthen the polymeric network. In this way, the polymeric network may suppress dendritic growth from the anode.
  • the anode may include exposed surfaces, where each exposed surface has alkali metal-containing nanostructures and/or microstructures, each of which may include the carbonaceous materials.
  • the anode may have three-dimensional (3D) structure, where some adjacent graphene sheets may intercalate alkali metal ions.
  • Another innovative aspect of the subject matter described in this disclosure may be implemented as a battery include an anode, a cathode, a protective sheath disposed on the cathode, a separator, and an electrolyte.
  • the anode may be arranged in a lattice configuration and include carbonaceous materials.
  • the cathode may be positioned opposite to the anode.
  • the separator may be disposed between the anode and cathode.
  • the protective sheath disposed on the cathode may include a tri-functional epoxy compound and a di-amine oligomer-based compound, both of which may chemically react with each other.
  • the protective sheath may prevent polysulfide migration within the battery based on chemical binding between the protective sheath and one or more lithium-containing poly sulfide intermediates.
  • the electrolyte may disperse within the cathode and contact the anode.
  • a polymeric network may be deposited over one or more exposed surfaces of the anode.
  • the polymeric network may have fluorinated polymer chains grafted with carbonaceous materials and be cross-linked with each another. In this way, the polymeric network may retain an alkali-metal containing fluoride, which in turn may suppress alkali metal dendrite formation associated with the anode.
  • cracks may extend into the cathode, where protective sheath may disperse throughout the one or more cracks.
  • the protective sheath may be arranged to reduce a susceptibility of the cathode to rupturing.
  • the protective sheath has a cross-linked, three-dimensional structure based on the tri-functional epoxy compound and the di-amine oligomer-based compound.
  • the tri-functional epoxy compound is one or more of trimethylolpropane triglycidyl ether (TMPTE), tris(4-hydroxyphenyl)methane triglycidyl ether, or tris(2, 3 -epoxypropyl) isocyanurate
  • the di-amine oligomer-based compound is one or more of dihydrazide sulfoxide (DHSO) or JEFFAMINE ® D-230 polyetheramine.
  • the protective sheath may include trimethylolpropane tris [poly (propylene glycol) and amine terminated ether.
  • the carbonaceous materials may include flat graphene, wrinkled graphene, a plurality of carbon nano-tubes (CNTs), and/or a plurality of carbon nano-onions (CNOs).
  • the cathode may include a host structure with one or more of flat graphene, wrinkled graphene, carbon nanotubes (CNTs), or carbon nano onions (CNOs), where the anode includes a solid lithium metal layer.
  • a tin fluoride layer may be disposed on the anode, and a lithium fluoride layer may be formed between the tin fluoride layer and the anode.
  • the lithium fluoride layer may be associated with chemical reactions between fluorine ions and lithium ions. In this way, the lithium fluoride layer may inhibit lithium-containing dendritic growth from the anode.
  • a solid-electrolyte interphase may be disposed on the anode.
  • the solid-electrolyte interphase may include tin, manganese, molybdenum, fluorine compounds, tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitrate, lithium phosphate, manganese oxide, and/or lithium lanthanum zirconium oxide (LLZO).
  • tin, manganese, molybdenum, fluorine compounds tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitrate, lithium phosphate, manganese oxide, and/or lithium lanthanum zirconium oxide (LLZO).
  • the battery may include an anode configured to output a plurality of lithium ions during cycling of the battery, a graded layer disposed on the anode, a cathode positioned opposite to the anode, an electrolyte dispersed throughout the cathode and the anode, and a separator positioned between the anode and cathode.
  • the graded layer may include a polymeric network including a density gradient formed of wrinkled graphene associated with graphene nanoplatelets dispersed throughout and isolated from one other within the polymeric network, at least some wrinkled graphene configured to expand in volume along one or more flexure points and retain polysulfides generated during cycling of the battery.
  • the polymeric network may include a plurality of fluorinated poly(meth)acrylates grafted onto one of more flexure points of at least some wrinkled graphene, a plurality of carbon-fluorine (C-F) bonds within the polymeric network, at least some of the plurality of carbon-fluorine (C-F) bonds configured to chemically react, by a Wurtz reaction, with at least some of the plurality of lithium ions and convert into carbon-lithium (C-Li) bonds by displacing fluorine ions (F ), a plurality of carbon-carbon (C-C) bonds formed during displacement of fluorine ions (F ) during the Wurtz reaction, formation of carbon-carbon (C-C) bonds associated with cross-linking of the polymeric network, and lithium fluoride (LiF) formed responsive to displacement of fluorine ions (F ), lithium fluoride (LiF) associated with consumption of at least some of the plurality of lithium ions.
  • C-F carbon-fluorine
  • the battery may also include a solid-electrolyte interphase formed at a surface of the anode exposed to the electrolyte during cycling of the battery.
  • the graded layer may be configured to grow the solid-electrolyte interphase during cycling of the battery.
  • the graded layer may be deposited on the anode by one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD).
  • the battery may include an anode configured to output a plurality of lithium ions during cycling of the battery, a graded layer disposed on the anode, a cathode positioned opposite to the anode, an electrolyte dispersed throughout the cathode and the anode, and a separator positioned between the anode and cathode.
  • the graded layer may include a polymeric network including a density gradient formed of wrinkled graphene associated with graphene nanoplatelets dispersed throughout and isolated from one other within the polymeric network, at least some wrinkled graphene configured to expand in volume along one or more flexure points and retain polysulfides generated during cycling of the battery.
  • the polymeric network may include a plurality of fluorinated poly(meth)acrylates grafted onto one of more flexure points of at least some wrinkled graphene, a plurality of carbon-fluorine (C-F) bonds within the polymeric network, at least some of the plurality of carbon-fluorine (C-F) bonds configured to chemically react with at least some of the plurality of lithium ions and convert into carbon-lithium (C-Li) bonds by displacing fluorine ions (F ), a plurality of carbon-carbon (C-C) bonds formed during displacement of fluorine ions (F-) during a Wurtz reaction, and lithium fluoride (LiF) formed responsive to formation of at least some of the plurality of carbon-carbon (C-C) bonds, where the lithium fluoride (LiF) may be associated with consumption of at least some of the plurality of lithium ions.
  • C-F carbon-fluorine
  • the first plurality of mesopores has a first mesopore density
  • the second plurality of mesopores has a second mesopore density different than the first mesopore density.
  • the first plurality of macropores has a first pore density
  • the second plurality of macropores has a second pore density different than the first pore density.
  • one or more of the first porous carbonaceous region or the second porous carbonaceous region may be configured to nucleate sulfur.
  • the cathode contains a plurality of pores, and may include a plurality of non-tri-zone particles, a plurality of tri-zone particles, a plurality of aggregates each including a multitude of the tri-zone particles joined together, a plurality of mesopores interspersed throughout the plurality of aggregates, a plurality of agglomerates each including a multitude of the aggregates joined to each other, and a plurality of macropores interspersed throughout the plurality of aggregates.
  • each tri zone particle may include a plurality of carbon fragments intertwined with each other and separated from one another by mesopores, and a deformable perimeter configured to coalesce with one or more adjacent non-tri-zone particles or tri-zone particles.
  • each aggregate may have a principal dimension in a range between 10 nanometers (nm) and 10 micrometers (pm)
  • each mesopore may have a principal dimension between 3.3 nanometers (nm) and 19.3 nm
  • each agglomerate may have a principal dimension in an approximate range between 0.1 mih and 1,000 mih
  • each macropore may have a principal dimension between 0.1 pm and 1,000 pm.
  • one or more of the first porous carbonaceous region or the second porous carbonaceous region may also include a selectively permeable shell configured to form a separated liquid phase on the first porous carbonaceous region or the second porous carbonaceous region, respectively.
  • the first porous carbonaceous region has an electrical conductivity in an approximate range between 500 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi).
  • the second porous carbonaceous region has an electrical conductivity in an approximate range between 0 S/m to 500 S/m at a pressure of 12,000 pounds per square in (psi).
  • one or more of the first plurality of agglomerates or second plurality of agglomerates may include aggregates connected to each other with one or more polymer-based binders.
  • each of the tri-zone particles may include a first porosity region located around a center of each of the tri-zone particles, the first porosity region including first pores, and a second porosity region surrounding the first porosity region, the second porosity region including second pores.
  • the first pores define a first pore density
  • the second pores define a second pore density different the first pore density.
  • the cathode may also include one or more additional porous carbonaceous regions, at least one additional porous carbonaceous region coupled with the second porous carbonaceous region. In some instances, one or more additional porous carbonaceous regions are arranged in order of incrementally decreasing concentration levels of carbonaceous materials away from the first porous carbonaceous region.
  • composition of matter including a plurality of pores.
  • the composition of matter may include a plurality of non-tri-zone particles, a plurality of aggregates, each aggregate including a multitude of the tri-zone particles joined together, each aggregate having a principal dimension in a range between 10 nanometers (nm) and 10 micrometers (pm), a plurality of mesopores interspersed throughout the plurality of aggregates, each mesopore having a principal dimension between 3.3 nanometers (nm) and 19.3 nm, a plurality of agglomerates, each agglomerate including a multitude of the aggregates joined to each other, each agglomerate having a principal dimension in an approximate range between 0.1 pm and 1,000 pm, and a plurality of macropores interspersed throughout the plurality of aggregates, each macropore having a principal dimension between 0.1 pm and 1,000 pm.
  • each tri-zone particle may include a plurality of carbon fragments intertwined with each other and separated from one another by mesopores, and a deformable perimeter configured to coalesce with one or more adjacent non-tri-zone particles or tri-zone particles in some aspects, each of the pores has a principal dimension in an approximate range between 0 nanometers (nm) and 32.3 nm. In other aspects, the composition of matter has an electrical conductivity in an approximate range between 100 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi).
  • the composition of matter may also include a selectively permeable shell configured to form a separated liquid phase on one or more exposed surfaces of the composition of matter.
  • the composition of matter may also include an electrolyte dispersed within the composition of matter.
  • at least some agglomerates are connected to each other with one or more polymer- based binders.
  • Figure 1 shows a diagram depicting an example battery, according to some implementations .
  • Figure 2 shows a diagram depicting another example battery, according to some implementations .
  • Figure 3 shows a diagram of an example electrode of a battery, according to some implementations .
  • Figure 4 shows a diagram a diagram of a portion of an example battery that includes a protective lattice, according to some implementations.
  • Figure 5 shows a diagram of an anode structure including a tin fluoride (SnF2) layer, according to some implementations.
  • Figure 6 shows a diagram of an enlarged portion of the anode structure of Figure 5, according to some implementations.
  • Figure 7 shows a diagram of a polymeric network of a battery, according to some implementations .
  • Figure 8A shows a diagram of an example carbonaceous particle with graded porosity, according to some implementations.
  • Figure 8B shows a diagram of an example of a tri-zone particle, according to some implementations.
  • Figure 8C shows an example step function representative of the tri-zone particle of Figure 8B, according to some implementations.
  • Figure 8D shows a graph depicting an example distribution of pore volume versus pore width of an example carbonaceous particle, according to some implementations.
  • Figures 9A and 9B show electron micrographs of example carbonaceous particles, aggregates, and/or agglomerates depicted in Figure 8A and/or Figure 8B, according to some implementations .
  • Figures 10A and 10B show transmission electron microscope (TEM) images of carbonaceous particles treated with carbon dioxide (CO2), according to some implementation.
  • TEM transmission electron microscope
  • Figure 11 shows a diagram depicting carbon porosity types prevalent in the anodes and/or the cathodes of the present disclosure, according to some implementations.
  • Figure 12 shows a graph depicting cumulative pore volume versus pore width for micropores and mesopores dispersed throughout the anode or cathode of a battery, according to some implementations.
  • Figure 13 shows graphs depicting battery performance per cycle number, according to some implementations.
  • Figure 14 shows a bar chart depicting capacity per cycle number, according to some implementations.
  • Figure 15 shows graphs depicting battery performance per cycle number, according to some implementations.
  • Figure 16 shows a graph depicting battery discharge capacity per cycle number, according to some implementations.
  • Figure 17 shows a graph depicting battery discharge capacity per cycle number, according to some implementations.
  • Figure 18 shows a graph depicting battery specific discharge capacity for various TBT-containing electrolyte mixtures, according to some implementations.
  • Figure 19 shows graphs depicting battery specific discharge capacity per cycle number for the battery of Figure 1, according to some implementations.
  • Figure 20 shows graphs depicting battery specific discharge capacity and discharge capacity retention per cycle number for the battery of Figure 2, according to other implementations .
  • Figure 21 shows graphs depicting battery specific discharge capacity and discharge capacity retention per cycle number for the battery of Figure 2, according to some other implementations.
  • Figure 22 shows a diagram of an example cathode of a battery, according to some implementations .
  • Batteries typically include several electrochemical cells that can be connected to each other to provide electric power to a wide variety of devices such as (but not limited to) mobile phones, laptops, electric vehicles (EVs), factories, and buildings.
  • Certain types of batteries such as lithium-ion or lithium-sulfur batteries, may be limited in performance by the type of electrolyte used or by uncontrolled battery side reactions.
  • optimization of the electrolyte may improve the cyclability, the specific discharge capacity, the discharge capacity retention, the safety, and the lifespan of a respective battery. For example, in an unused or “fresh” battery, lithium ions are transported freely from the anode to the cathode upon activation and later during initial and subsequent discharge cycles.
  • lithium ions may be forced to migrate back from their electrochemically favored positions in the cathode to the anode, where they are stored for subsequent use.
  • This cyclical discharge-charge process associated with rechargeable batteries can result in the generation of undesirable chemical species that can interfere with the transport of lithium ions to and from the cathode during respective discharge and charge of the battery.
  • lithium-containing polysulfide intermediate species referred to herein as “polysulfides” are generated when lithium ions interact with elemental sulfur (or, in some configurations, lithium sulfide, LriS) present in the cathode.
  • polysulfides are soluble in the electrolyte and, as a result, diffuse throughout the battery during operational cycling, thereby resulting in loss of active material from cathode. Generation of excessive concentration levels of polysulfides can result in unwanted battery capacity decay and cell failure during operational cycling, potentially reducing the driving range for electric vehicles (EVs) and increasing the frequency with which such EVs need recharging.
  • SEI solid electrolyte interphase
  • polysulfides participate in the formation of inorganic layers in a solid electrolyte interphase (SEI) provided in the battery.
  • SEI solid electrolyte interphase
  • the anode may be protected by a stable inorganic layer formed in the electrolyte and containing 0.020 M L1 2 S 5 (0.10 M sulfur) and 5.0 wt.
  • the anode with a lithium fluoride and polysulfides may enrich the SEI and result in a stable Coulombic efficiency of 95% after 233 cycles for Li-Cu half cells, while preventing formation of lithium dendrites or other uncontrolled lithium growths that can extend from the anode to the cathode and result in a failed or ruptured cell.
  • polysulfides are generated at certain concentrations (such as greater than 0.50 M sulfur)
  • formation of the SEI may be hindered.
  • lithium metal from the anode may be undesirably etched, creating a rough and imperfect surface exposed to the electrolyte. This unwanted deterioration (etching) of the anode due to a relatively high concentration of polysulfides may indicate that polysulfide dissolution and diffusion may be limiting battery performance.
  • the porosity of a carbonaceous cathode may be adjusted to achieve a desired balance between maximizing energy density and inhibiting the migration of poly sulfides into and/or throughout the battery’s electrolyte.
  • carbonaceous may refer to materials containing or formed of one or more types or configuration of carbon.
  • cathode porosity may be higher in sulfur and carbon composite cathodes than in conventional lithium-ion battery electrodes. Denser electrodes with relatively low porosity may minimize electrolyte intake, parasitic weight, and cost. Sulfur utilization may be limited by the solubility of polysulfides and conversion from those polysulfides into lithium sulfide (Li 2 S).
  • the conversion of poly sulfides into lithium sulfide may be based on the accessible surface area of the cathode.
  • cathode porosity may be adjusted based on electrolyte constituent materials to maximize battery volumetric energy density.
  • one or more protective layers or regions can be added to surfaces of the cathode and/or the anode exposed to the electrolyte to adjust cathode porosity levels. In some aspects, these protective layers or regions can inhibit the undesirable migration of polysulfides throughout the battery.
  • the lithium- sulfur battery including a liquid-phase electrolyte, which may include a ternary solvent package and one or more additives.
  • the lithium- sulfur battery may include a cathode, an anode positioned opposite to the cathode, and an electrolyte.
  • the cathode may include several regions, where each region may be defined by two or more carbonaceous structures adjacent to and in contact with each other.
  • the electrolyte may be interspersed throughout the cathode and in contact with the anode.
  • the electrolyte may include a ternary solvent package and 4,4’-thiobisbenzenethiol (TBT).
  • the electrolyte may include the ternary solvent package and 2- mercaptobenzothiazole (MBT).
  • the ternary solvent package may include 1,2- Dimethoxyethane (DME), 1,3-Dioxolane (DOL), tetraethylene glycol dimethyl ether (TEGDME) and one or more additives, which may include a lithium nitrate (L1NO3), all which may be in a liquid-phase.
  • the ternary solvent package may be prepared by mixing approximately 5,800 microliters (pL) of DME, 2,900 microliters (pL) of DOL, and 1,300 microliters (pL) of TEGDME with one another to create a mixture.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • the ternary solvent package may be prepared with 2,000 microliters (pL) of DME, 8,000 microliters (pL) of DOL, and 2,000 microliters (pL) of TEGDME and include approximately 0.01 mol of dissolved lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).
  • the ternary solvent package may be prepared at a first approximate dilution level of 1 molar (M) LiTFSI in a mixture of DME:DOL:TEGDME.
  • the ternary solvent package may be prepared at a second approximate dilution level of approximately 1 M LiTFSI in DME:DOL:TEGDME at an approximate volume ratio of 1:4:1 and include either an addition of 5M TBT solution or an addition of 5M MBT solution, or an addition of other additives and/or chemical substances.
  • each carbonaceous structure may include a relatively high-density outer shell region and a relatively low-density core region.
  • the core region may be formed within an interior portion of the outer shell region.
  • the outer shell region may have a carbon density between approximately 1.0 grams per cubic centimeter (g/cc) and 3.5 g/cc.
  • the core region may have a carbon density of between approximately 0.0 g/cc and 1.0 g/cc or some other range lower than the first carbon density.
  • each carbonaceous structure may include an outer shell region and core region having the same or similar densities, for example, such that the carbonaceous structure does not include a graded porosity.
  • Various regions of the cathode may include microporous channels, mesoporous channels, and macroporous channels interconnected to each other to form a porous network extending from the outer shell region to the core region.
  • the porous network may include pores that each have a principal dimension of approximately 1.5 nm.
  • one or more portions of the porous network may temporarily micro-confine electroactive materials such as (but not limited to) elemental sulfur within the cathode, which may increase battery specific capacity by complexing with lithium ions.
  • the ternary solvent package may have a tunable polarity, a tunable solubility, and be capable of transporting lithium ions.
  • the ternary solvent package may at least temporarily suspend polysulfides (PS) during charge-discharge cycles of the battery.
  • the porous network formed by the interconnection of microporous, mesoporous, and macroporous channels within the cathode may include a plurality of pores having a multitude of different pore sizes.
  • the plurality of pores may include micropores having a pore size less than approximately 2 nm, may include mesopores having a pore size between approximately 5 and 50 nm, and may include macropores having a pore size greater than approximately 50 nm.
  • the micropores, mesopores, and macropores may collectively mitigate the undesirable migration or diffusion of poly sulfides throughout the electrolyte. Since the polysulfide shuttle effect may result in the loss of active material from the cathode, the ability to mitigate or reduce the polysulfide shuttle effect can increase battery performance.
  • the micropores may have a pore size of approximately 1.5 nm selected to micro-confine elemental sulfur (Sg, or smaller chains/fragments of sulfur, for example in the form of S2,S4 or S 6 ) pre-loaded into the cathode.
  • the micro-confinement of elemental sulfur within the cathode may allow TBT or MBT complexes generated during battery cycling to inhibit the migration of long-chain polysulfides within the mesopores of the cathode. Accumulation of these long-chain polysulfides within the mesopores of the cathode may cause the cathode to volumetrically expand to retain the polysulfides and thereby reduce the polysulfide shuttle effect.
  • lithium ions may continue to transport freely between the anode and the cathode via the electrolyte without being blocked or impeded by the polysulfides.
  • the free movement of lithium ions throughout the electrolyte without interference by polysulfides can increase battery performance.
  • one or more protective layers, sheaths, films, and/or regions may be disposed on the anode and/or the cathode and/or the separator and in contact with the electrolyte.
  • the protective layers may include materials capable of binding with polysulfides to impede poly sulfide migration and prevent lithium dendrite formation.
  • the protective layers may be arranged in different configurations and used with any of the electrolyte chemistries and/or compositions disclosed herein, which in turn may result in complete tunability of the battery.
  • carbonaceous materials may be grafted with fluorinated polymer chains and deposited on one or more exposed surfaces of the anode.
  • the fluorinated polymer chains can be cross-linked into a polymeric network on contact with Lithium metal from the anode surface via the Wurtz reaction.
  • the cross-linked polymeric network formation may, in turn, suppress Lithium metal dendrite formation associated with the anode, and may also generate Lithium fluoride.
  • Fluorinated polymers within the polymeric network may participate in chemical reactions during battery operational cycling to yield Lithium fluoride. Formation of the lithium fluoride may involve the chemical binding of lithium ions from the electrolyte with fluorine ions.
  • the polymeric network may be combined with any of the electrolyte chemistries and/or compositions disclosed herein and/or a protective sheath disposed on the cathode.
  • the protective sheath can be formed by combining compounds containing di-functional, or higher functionality Epoxy and Amine or Amide compounds. Their intermolecular cross-linking would result in formation of 3D network with high chemical resistance to dissolution in electrolyte.
  • Composition may include a tri-functional epoxy compound and a di-amine oligomer-based compound, which may react with each other to produce a protective lattice that can bind to polysulfides generated in the cathode and prevent their migration or diffusion into the electrolyte.
  • the protective lattice may diffuse through one or more cracks that may form in the cathode due to battery cycling. The protective lattice, when diffused throughout such cracks formed in the cathode, may increase the structural integrity of the cathode, and reduce potential rupture of the cathode associated with volumetric expansion.
  • one or more of the disclosed battery components may be combined with a conformal coating disposed on edges or surfaces of the anode exposed to the electrolyte.
  • the conformal coating may include a graded interface layer that may replace the polymeric network.
  • the graded interface layer may include a tin fluoride layer and a tin-lithium alloy region formed between the tin fluoride layer and the anode. The tin-lithium alloy region may form a layer of lithium fluoride uniformly dispersed between the anode and the tin-fluoride layer in response to operational cycling of the battery.
  • a lithium- sulfur battery employing various aspects of the present disclosure may include an electroactive material extracted from an external source, e.g., a subterranean source and/or an extraterrestrial subterranean source.
  • the cathode may be prepared as a sulfur-free cathode including functional pores that may micro-confine the electroactive material within the cathode.
  • the cathode may include aggregates including a multitude of carbonaceous particles joined together, and may include agglomerates including a multitude of the aggregates joined together.
  • the carbonaceous materials used to form the cathode (and/or the anode) may be tuned to define unique pore sizes, size ranges, and volumes.
  • the carbonaceous particles may include non-tri-zone particles with and without tri-zone particles. In other implementations, the carbonaceous particles may not include tri-zone particles.
  • Each tri-zone particle may include micropores, mesopores, and macropores, and both the non-tri-zone and tri-zone particles may each have a principal dimension in an approximate range of 20 nm to 300 nm.
  • Each of the carbonaceous particles may include carbonaceous fragments nested within each other and separated from immediate adjacent carbonaceous fragments by mesopores. In some aspects, each of the carbonaceous particles may have a deformable perimeter that changes in shape and coalesces with adjacent materials.
  • pores may be distributed throughout the plurality of carbonaceous fragments and/or the deformable perimeters of the carbonaceous particles.
  • mesopores may be interspersed throughout the aggregates, and macropores may be interspersed throughout the plurality of agglomerates.
  • each mesopore may have a principal dimension between 3.3 nanometers (nm) and 19.3 nm
  • each aggregate may have a principal dimension in an approximate range between 10 nm and 10 micrometers (pm)
  • each agglomerate may have a principal dimension in an approximate range between 0.1 pm and 1,000 pm.
  • specific combinations of pore sizes matched with unique electrolyte formulations and protective layers can be used to reduce or mitigate the harmful effects of unwanted polysulfide diffusion, which may further increase battery performance.
  • FIG. 1 shows an example battery 100, according to some implementations.
  • the battery 100 may be a lithium- sulfur electrochemical cell, a lithium-ion battery, or a lithium- sulfur battery.
  • the battery 100 may have a body 105 that includes a first substrate 101, a second substrate 102, a cathode 110, an anode 120 positioned opposite to the cathode 110, and an electrolyte 130.
  • the first substrate 101 may function as a current collector for the anode 120
  • the second substrate 102 may function as a current collector for the cathode 110.
  • the cathode 110 may include a first thin film 111 deposited onto the second substrate 102, and may include a second thin film 112 deposited onto the first thin film 111.
  • the electrolyte 130 may be a liquid-phase electrolyte including one or more additives such as lithium nitrate, tin fluoride, lithium iodide, lithium bis(oxalate)borate (LiBOB), cesium nitrate, cesium fluoride, ionic liquids, lithium fluoride, fluorinated ether, TBT, MBT, DPT and/or the like.
  • Suitable solvent packages for these example additives may include various dilution ratios, including 1:1:1 of 1,3-dioxolane (DOL), 1 ,2-dimethoxy ethane, (DME), tetraethylene glycol dimethyl ether (TEGDME), and/or the like.
  • a lithium layer may be electrodeposited on one or more exposed carbon surfaces of the anode 120.
  • the lithium layer may include elemental lithium provided by the ex-situ electrodeposition of lithium onto exposed surfaces of the anode 120.
  • the lithium layer may include lithium, calcium, potassium, magnesium, sodium, and/or cesium, where each metal may be ex-situ deposited onto exposed carbon surfaces of the anode 120.
  • the lithium layer may provide lithium ions available for transport to-and-from the cathode 110 during operational cycling of the battery 100. As a result, the battery 100 may not need an additional lithium source for operation.
  • elemental sulfur may be pre-loaded in various pores or porous networks formed in the cathode 110.
  • the elemental sulfur may form lithium-sulfur complexes that can micro-confine (at least temporarily) greater amounts of lithium than conventional cathode designs.
  • the battery 100 may outperform batteries that rely on such conventional cathode designs.
  • the lithium layer may dissociate and/or separate into lithium ions 125 and electrons 174 during a discharge cycle of the battery 100.
  • the lithium ions 125 may migrate from the anode 120 towards the cathode 110 through the electrolyte 130 to their electrochemically favored positions within the cathode 110, as depicted in the example of Figure 1.
  • electrons 174 are released from lithium ions 125 and become available to carry charge, and therefore conduct an electric current, between the anode 120 and cathode 110.
  • the electrons 174 may travel from the anode 120 to the cathode 110 through an external circuit to power a load 172.
  • the load 172 may be any suitable circuit, device, or system such as (but not limited to) a lightbulb, consumer electronics, or an electric vehicle (EV).
  • the battery 100 may include a solid-electrolyte interphase layer 140.
  • the solid-electrolyte interphase layer 140 may, in some instances, be formed artificially on the anode 120 during operational cycling of the battery 100. In such instances, the solid-electrolyte interphase layer 140 may also be referred to as an artificial solid-electrolyte interphase, or A-SEI.
  • the solid-electrolyte interphase layer 140 when formed as an A-SEI, may include tin, manganese, molybdenum, and/or fluorine compounds. Specifically, the molybdenum may provide cations, and the fluorine compounds may provide anions.
  • the cations and anions may interact with each other to produce salts such as tin fluoride, manganese fluoride, silicon nitride, lithium nitride, lithium nitrate, lithium phosphate, manganese oxide, lithium lanthanum zirconium oxide ( LLZO , LivLa 3 Zr 2 0i 2 ), etc.
  • the A-SEI may be formed in response to exposure of lithium ions 125 to the electrolyte 130, which may include solvent-based solutions including tin and/or fluorine.
  • the solid-electrolyte interphase layer 140 may be artificially provided on the anode 120 prior to activation of the battery 100. Alternatively, in one implementation, the solid-electrolyte interphase layer 140 may form naturally, e.g., during operational cycling of the battery 100, on the anode 120. In some instances, the solid- electrolyte interphase layer 140 may include an outer layer of shielding material that can be applied to the anode 120 as a micro-coating.
  • formation of the solid-electrolyte interphase layer 140 on portions of the anode 120 facing the electrolyte 130 may result from electrochemical reduction of the electrolyte 130, which in turn may reduce uncontrolled decomposition of the anode 120.
  • the battery 100 may include a barrier layer 142 that flanks the solid-electrolyte interphase layer 140, for example, as shown in Figure 1.
  • the barrier layer 142 may include a mechanical strength enhancer 144 coated and/or deposited on the anode 120.
  • the mechanical strength enhancer 144 may provide structural support for the battery 100, may prevent lithium dendrite formation from the anode 120, and/or may prevent protrusion of lithium dendrite throughout the battery 100.
  • the mechanical strength enhancer 144 may be formed as a protective coating over the anode 120, and may include one or more carbon allotropes, carbon nano onions (CNOs), nanotubes (CNTs), reduced graphene oxide, graphene oxide (GO), and/or carbon nano-diamonds.
  • the solid-electrolyte interphase layer 140 may be formed within the mechanical strength enhancer 144.
  • the first substrate 101 and/or the second substrate 102 may be a solid copper metal foil and may influence the energy capacity, rate capability, lifespan, and long-term stability of the battery 100.
  • the first substrate 101 and/or the second substrate 102 may be subject to etching, carbon coating, or other suitable treatment to increase electrochemical stability and/or electrical conductivity of the battery 100.
  • the first substrate 101 and/or the second substrate 102 may include or may be formed from a selection of aluminum, copper, nickel, titanium, stainless steel and/or carbonaceous materials depending on end-use applications and/or performance requirements of the battery 100.
  • the first substrate 101 and/or the second substrate 102 may be individually tuned or tailored such that the battery 100 meets one or more performance requirements or metrics.
  • the first substrate 101 and/or the second substrate 102 may be at least partially foam-based or foam-derived, and can be selected from any one or more of metal foam, metal web, metal screen, perforated metal, or sheet-based three-dimensional (3D) structures.
  • the first substrate 101 and/or the second substrate 102 may be a metal fiber mat, metal nanowire mat, conductive polymer nanofiber mat, conductive polymer foam, conductive polymer-coated fiber foam, carbon foam, graphite foam, or carbon aerogel.
  • first substrate 101 and/or second substrate 102 may be carbon xerogel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber foam, graphite fiber foam, exfoliated graphite foam, or any combination thereof.
  • FIG. 2 shows another example battery 200, according to some implementations.
  • the battery 200 may be similar to the battery 100 of Figure 1 in many respects, such that description of like elements is not repeated herein.
  • the battery 200 may be a next-generation battery, such as a lithium-metal battery and/or a solid-state battery featuring a solid-state electrolyte.
  • the battery 200 may include a liquid-phase electrolyte 230 and may therefore include any of the protective layers and/or electrolyte chemistries or compositions disclosed herein.
  • the electrolyte 230 may be solid or substantially solid.
  • the electrolyte 230 may begin in a gel phase and then later solidify upon activation of the battery 200.
  • the battery 200 may reduce specific capacity or energy losses associated with the polysulfide shuttle effect by replacing conventional carbon scaffolded anodes with a single solid metal layer of lithium deposited in an initially empty cavity.
  • the anode 120 of the battery 100 of Figure 1 may include carbon scaffolds
  • the anode 220 of the battery 200 of Figure 2 may be a lithium- metal anode devoid of any carbon material.
  • the lithium-metal anode may be formed as a single solid lithium metal layer and referred to as a “lithium metal anode.”
  • Energy density gains associated with various cathode materials may be based on whether lithium metal is pre-loaded into the cathode 210 and/or is prevalent in the electrolyte 230.
  • Either the cathode 210 and/or the electrolyte 230 may provide lithium available for lithiation of the anode 220.
  • batteries having high-capacity cathodes may need thicker or energetically denser anodes in order to supply the increased quantities of lithium needed for usage by the high-capacity cathodes.
  • the anode 220 may include scaffolded carbonaceous structures capable of being incrementally filled with lithium deposited therein.
  • These carbonaceous structures may be capable of retaining greater amounts of lithium within the anode 220 as compared to conventional graphitic anodes, which may be limited to solely hosting lithium intercalated between alternating graphene layers or may be electroplated with lithium.
  • conventional graphitic anodes may use six carbon atoms to hold a single lithium atom.
  • batteries disclosed herein may reduce or even eliminate carbon use in the anode 220, which may allow the anode 220 to store greater amounts of lithium in a relatively smaller volume than conventional graphitic anodes. In this way, the energy density of the battery 200 may be greater than conventional batteries of a similar size.
  • Lithium metal anodes such as the anode 220, may be prepared to function with a solid-state electrolyte designed to inhibit the formation and growth of lithium dendrites from the anode.
  • a separator 250 may further limit dendrite formation and growth.
  • the separator 250 may have a similar ionic conductivity as the electrolyte 130 of Figure 1 yet still reduce lithium dendrite formation.
  • the separator 250 may be formed from a ceramic containing material and may, as a result, fail to chemically react with metallic lithium. As a result, the separator 250 may be used to control lithium ion transport through pores dispersed across the separator 250 while concurrently preventing a short-circuit by impeding the flow or passage of electrons through the electrolyte 230.
  • a void space (not shown for simplicity) may be formed within the battery 200 at or near the anode 220. Operational cycling of the battery 200 in this implementation may result in the deposition of lithium into the void space. As a result, the void space may become or transform into a lithium-containing region (such as a solid lithium metal layer) and function as the anode 220. In some aspects, the void space may be created in response to chemical reactions between a metal-containing electrically inactive component and a graphene-containing component of the battery 200. Specifically, the graphene- containing component may chemically react with lithium deposited into the void space during operational cycling and produce lithiated graphite (LiCe) or a patterned lithium metal.
  • LiCe lithiated graphite
  • the lithiated graphite produced by the chemical reactions may generate or lead to the generation and/or liberation of lithium ions and/or electrons that can be used to carry electric charge or a “current” between the anode 220 and the cathode 210 during discharge cycles of the battery 200.
  • the battery 200 may be able to hold more electroactive material and/or lithium per unit volume (as compared to batteries with scaffolded carbon and/or intercalated lithiated graphite anodes).
  • the anode 220 when prepared as a solid lithium metal layer, may result in the battery 200 having a higher energy density and/or specific capacity than batteries with scaffolded carbon and/or intercalated lithiated graphite anodes, thereby resulting in longer discharge cycle times and additional power output per unit time.
  • the electrolyte 230 of the battery 200 of Figure 2 may be prepared with any of the liquid-phase electrolyte chemistries and/or compositions disclosed herein.
  • the electrolyte 230 may include lithium and/or lithium ions available for cyclical transport from the anode 220 to the cathode 210 and vice-versa during discharge and charge cycles, respectively.
  • the battery 200 may include one or more unique polysulfide retention features. For example, given that polysulfides are soluble in the electrolyte 230, some polysulfides may be expected to drift or migrate from the cathode 210 towards the anode 220 due to differences in electrochemical potential, chemical gradients, and/or other phenomena.
  • lithium ions 225 may be transported from one or more start positions 226 in or near the anode 220 along transport pathways to one or more end positions 227 in or near the cathode 210, as depicted in the example of Figure 2.
  • a polymeric network 285 may be disposed on the anode 220 to reduce the uncontrolled migration of poly sulfides 282 from the anode 220 to the cathode 210.
  • the polymeric network 285 may include one or more layers of carbonaceous materials grafted with fluorinated polymer chains cross-linked with each other via the Wurtz reaction upon exposure to Lithium anode surface.
  • C-F bonds may chemically react with lithium metal from the surface of the anode 220 to produce highly ionic Carbon- Lithium bonds (C-Li). These formed C-Li bonds, in turn, may react with C-F bonds of polymer chains to form new Carbon-Carbon bonds that can also cross-link the polymer chains into (and thereby form) the polymeric network and generate lithium fluoride (LiF).
  • the resulting lithium fluoride may be uniformly distributed along the entire perimeter of the polymeric network 285, such that lithium ions are uniformly consumed to produce an interface layer 283 that may form or otherwise include lithium fluoride during battery cycling.
  • the interface layer 283 may extend along a surface or portion of the anode 220 facing the cathode 210, as shown in Figure 2.
  • the lithium ions 225 are less likely to combine and/or react with each other and are more likely to combine and/or react with fluorine atoms made available by the fluorinated polymer chains in the polymeric network 285.
  • the resulting reduction of lithium- lithium chemical reactions decreases lithium-lithium bonding responsible for undesirable lithium-metal dendrite formation.
  • the polymeric network 285 may replace the interphase layer 240 that either naturally or artificially develops between the anode 220 and the electrolyte 230.
  • the interface layer 283 of the polymeric network 285 is in contact with the anode 220, and a protective layer 284 is disposed on top of the interface layer 283 (such as between the interface layer 283 and the interphase layer 240).
  • the interface layer 283 and the protective layer 284 may collectively define a gradient of cross-linked fluoropolymer chains of varying degrees of density, for example, as described with reference to Figure 7.
  • the battery 200 may include a protective lattice 280 disposed on the cathode 210.
  • the protective lattice 280 may include a tri-functional epoxy compound and a di-amine oligomer-based compound that may chemically react with each other to produce nitrogen and oxygen atoms.
  • the nitrogen and oxygen atoms made available by the protective lattice 280 can bind with the polysulfides 282, thereby confining the polysulfides 282 within the cathode 210 and/or the protective lattice 280.
  • Either of the cathode 210 and/or the protective lattice 280 may include carbon-carbon bonds and/or regions capable of flexing and/or volumetrically expanding during operational cycling of the battery 200, which may confine polysulfides 282 generated during the operational cycling to the cathode 210.
  • the electrolyte 130 of Figure 1 and the electrolyte 230 of Figure 2 may be prepared according to one or more recipes disclosed herein.
  • a ternary solvent package used in the electrolyte 130 and/or the electrolyte 230 may include DME, DOF and TEGDME.
  • a solvent mixture may be prepared by mixing 5800 pL DME, 2900 pL DOL and 1300 pL TEGDME and stirring at room temperature (77°F or 25°C). Next, 0.01 mol (2,850.75 mg) of LiTFSI may be weighed.
  • LiTFSI LiTFSI
  • solvent mixture by stirring at room temperature to prepare approximately 10 mL 1 M LiTFSI in DME:DOL:TEGDME (volume: volume: volume 1:4:1).
  • a ternary solvent package used in the electrolyte 130 and/or the electrolyte 230 may include DME, DOL, TEGDME, and TBT or MBT.
  • a solvent mixture may be prepared by mixing 2,000 pL DME, 8,000 pL DOL and 2,000 pL TEGDME and stirring at room temperature (68°F or 25°C). Next, 0.01 mol (2,850.75 mg) of LiTFSI may be weighed and dissolved in approximately 3 mL of the solvent mixture by stirring at room temperature.
  • the dissolved LiTFSI and an additional solvent mixture may be mixed in a 10 mL volumetric flask to produce approximately 1 M LiTFSI in DME:DOL:TEGDME (volume: volume: volume 1:4:1).
  • approximately 0.05 mmol (-12.5 mg) TBT or MBT may be added to the 10 mL solution to produce 10 mL of 5M TBT or MBT solution.
  • FIG 3 shows an example electrode 300, according to some implementations.
  • the electrode 300 may be one example of the cathode 110 and/or the anode 120 of the battery 100 of Figure 1.
  • the electrode 300 may be one example of the cathode 210 of the battery 200 of Figure 2.
  • the electrode 300 may temporarily micro-confine an electroactive material, such as elemental sulfur, which may decrease the amount of sulfur available for reacting with lithium to produce polysulfides.
  • the electrode 300 may provide an excess supply of lithium and/or lithium ions that can compensate for first-cycle operational losses associated with lithium-based batteries.
  • the electrode 300 may be porous and receptive of a liquid-phase electrolyte, such as the electrolyte 130 of Figure 1. Electroactive species, such as lithium ions 125 suspended in the electrolyte 130, may chemically react with elemental sulfur pre-loaded into pores of the electrode 300 to produce polysulfides, which in turn may be trapped in the electrode 300 during battery cycling. In some aspects, the electrode 300 may expand in volume along one or more flexure points to retain additional quantities of polysulfides created during battery cycling.
  • lithium ions 125 may flow freely through the electrolyte 130 from the anode 120 to the cathode 110 during discharge cycles of the battery 100 (e.g., without being impeded by the poly sulfides).
  • lithium ions 125 reach the cathode 110 and react with elemental sulfur contained in or associated with the cathode 110, sulfur is reduced to lithium polysulfides (LiaSt) at decreasing chain lengths according to the order LLSs LhSe L12S4 ® Lt2S2 Li S. where 2 ⁇ x ⁇ 8).
  • the electrode 300 may include a body 301 defined by a width 305, and may include a first thin film 310 and a second thin film 320.
  • the first thin film 310 may include a plurality of first aggregates 312 that join together to form a first porous structure 316 of the electrode 300.
  • the first porous structure 316 may have an electrical conductivity between approximately 0 and 500 S/m. In other instances, the first electrical conductivity may be between approximately 500 and 1,000 S/m. In some other instances, the first electrical conductivity may be greater than 1,000 S/m.
  • the first aggregates 312 may include carbon nano-tubes (CNTs), carbon nano-onions (CNOs), flaky graphene, crinkled graphene, graphene grown on carbonaceous materials, and/or graphene grown on graphene.
  • the first aggregates 312 may be decorated with a plurality of first nanoparticles 314.
  • the first nanoparticles 314 may include tin, lithium alloy, iron, silver, cobalt, semiconducting materials and/or metals such as silicon and/or the like.
  • CNTs due to their ability to provide high exposed surface areas per unit volume and stability at relatively high temperatures (such as above 77°F or 25°C), may be used as a support material for the first nanoparticles 314.
  • the first nanoparticles 314 may be immobilized (such as by decoration, deposition, surface modification or the like) onto exposed surfaces of CNTs and/or other carbonaceous materials.
  • the first nanoparticles 314 may react with chemically available carbon on exposed surfaces of the CNTs and/or other carbonaceous materials.
  • the second thin film 320 may include a plurality of second aggregates 322 that join together to form a second porous structure 326.
  • the electrical conductivities of the first porous structure 316 and/or the second porous structure 326 may be between approximately 0 S/m and 250 S/m.
  • the first porous structure 316 may have a higher electrical conductivity than the second porous structure 326.
  • the first electrical conductivity may be between approximately 250 S/m and 500 S/m, while the second electrical conductivity may be between approximately 100 S/m and 250 S/m.
  • the second electrical conductivity may be between approximately 250 S/m and 500 S/m. In yet another implementation, the second electrical conductivity may be greater than 500 S/m.
  • the second aggregates 322 may include CNTs, CNOs, flaky graphene, crinkled graphene, graphene grown on carbonaceous materials, and/or graphene grown on graphene. [0105] The second aggregates 322 may be decorated with a plurality of second nanoparticles 324. In some implementations, the second nanoparticles 324 may include iron, silver, cobalt, semiconducting materials and/or metals such as silicon and/or the like.
  • CNTs may also be used as a support material for the second nanoparticles 324.
  • the second nanoparticles 324 may be immobilized (such as by decoration, deposition, surface modification or the like) onto exposed surfaces of CNTs and/or other carbonaceous materials.
  • the second nanoparticles 324 may react with chemically available carbon on exposed surfaces of the CNTs and/or other carbonaceous materials.
  • the first thin film 310 and/or the second thin film 320 may be created as a layer or region of material and/or aggregates.
  • the layer or region may range from fractions of a nanometer to several microns in thickness, such as between approximately 0 and 5 microns, between approximately 5 and 10 microns, between approximately 10 and 15 microns, or greater than 15 microns.
  • Any of the materials and/or aggregates disclosed herein, such as CNOs may be incorporated into the first thin film 310 and/or the second thin film 320 to result in the described thickness levels.
  • the first thin film 310 may be deposited onto the second substrate 102 of Figure 1 by chemical deposition, physical deposition, or grown layer-by- layer through techniques such as Frank-van der Merwe growth, Stranski-Krastonov growth, Volmer-Weber growth and/or the like.
  • the first thin film 310 may be deposited onto the second substrate 102 by epitaxy or other suitable thin-film deposition process involving the epitaxial growth of materials.
  • the second thin film 320 and/or subsequent thin films may be deposited onto their respective immediately preceding thin film in a manner similar to that described with reference to the first thin film 310.
  • each of the first aggregates 312 and/or the second aggregates 322 may be a relatively large particle formed by many relatively small particles bonded or fused together.
  • the external surface area of the relatively large particle may be significantly smaller than combined surface areas of the many relatively small particles.
  • the forces holding an aggregate together may be, for example, covalent, ionic bonds, or other types of chemical bonds resulting from the sintering or complex physical entanglement of former primary particles.
  • first aggregates 312 may join together to form the first porous structure 316
  • second aggregates 322 may join together to form the second porous structure 326.
  • the electrical conductivity of the first porous structure 316 may be based on the concentration level of the first aggregates 312 within the first porous structure 316
  • the electrical conductivity of the second porous structure 326 may be based on the concentration level of the second aggregates 322 within the second porous structure 326.
  • the concentration level of the first aggregates 312 may cause the first porous structure 316 to have a relatively high electrical conductivity
  • the concentration level of the second aggregates 322 may cause the second porous structure 326 to have a relatively low electrical conductivity (such that the first porous structure 316 has a greater electrical conductivity than the second porous structure 326).
  • the resulting differences in electrical conductivities of the first porous structure 316 and the second porous stmcture 326 may create an electrical conductivity gradient across the electrode 300.
  • the electrical conductivity gradient may be used to control or adjust electrical conduction throughout the electrode 300 and/or one or more operations of the battery 100 of Figure 1.
  • the relatively small source particles may be referred to as “primary particles,” and the relatively large aggregates formed by the primary particles may be referred to as “secondary particles.”
  • the primary particles may be or include multiple graphene sheets, layers, regions, and/or nanoplatelets fused and/or joined together.
  • carbon nano-onions CNOs
  • CNTs carbon nano-tubes
  • some aggregates may have a principal dimension (such as a length, a width, and/or a diameter) between approximately 500 nm and 25 pm.
  • aggregates may include innately- formed smaller collections of primary particles, referred to as “innate particles,” of graphene sheets, layers, regions, and/or nanoplatelets joined together at orthogonal angles.
  • innate particles may each have a respective dimension between approximately 50 nm and 250 nm.
  • the surface area and/or porosity of these innate particles may be imparted by secondary processes, such as carbon-activation by a thermal, plasma, or combined thermal- plasma process using one or more of steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnC12, H3P04, or other similar chemical agents alone or in combination.
  • the first porous stmcture 316 and/or the second porous structure 326 may be produced from a carbonaceous gaseous species that can be controlled by gas-solid reactions under non-equilibrium conditions.
  • Producing the first porous stmcture 316 and/or the second porous structure 326 in this manner may involve recombination of carbon- containing radicals formed from the controlled cooling of carbon-containing plasma species (which can be generated by excitement or compaction of feedstock carbon-containing gaseous and/or plasma species in a suitable chemical reactor).
  • the first aggregates 312 and/or the second aggregates 322 may have a percentage of carbon to other elements, except hydrogen, within each respective aggregate of greater than 99%. In some instances, a median size of each aggregate may be between approximately 0.1 microns and 50 microns.
  • the first aggregates 312 and/or the second aggregates 322 may also include metal organic frameworks (MOFs).
  • the first porous structure 316 and second porous structure 326 may collectively define a host structure 328, for example, as shown in Figure 3.
  • the host structure 328 may be based on a carbon scaffold and/or may include decorated carbons, for example, as shown in Figure 8.
  • the host structure 328 may provide structural definition to the electrode 300.
  • the host stmcture 328 may be fabricated as a positive electrode and used in the cathode 110 of Figure 1.
  • the host structure 328 may be fabricated as a negative electrode and used in the anode 120 of Figure 1.
  • the host structure 328 may include pores having different sizes, such as micropores, mesopores, and/or macropores defined by the IUPAC.
  • the micropores may have a width of approximately 1.5 nm, which may be large enough to allow sulfur to be pre-loaded into the electrode 300 and yet small enough to confine polysulfides within the electrode 300.
  • the host structure 328 when provided within the electrode 300 as shown in Figure 3, may include microporous, mesoporous, and/or macroporous pathways created by exposed surfaces and/or contours of the first porous structure 316 and/or the second porous structure 326. These pathways may allow the host structure 328 to receive an electrolyte, for example, by transporting lithium ions towards the cathode 110 of the battery 100.
  • the electrolyte 130 may infiltrate the various porous pathways of the host structure 328 and uniformly disperse throughout the electrode 300 and/or other portions of the battery 100. Infiltration of the electrolyte 130 into such regions of the host structure 328 may allow the lithium ions 125 migrating from the anode 120 towards the cathode 110 to react with elemental sulfur associated with the cathode 110 to form lithium- sulfur complexes. As a result, the elemental sulfur may retain additional quantities of lithium ions that would otherwise be achievable using non-sulfur chemistries such as lithium cobalt oxide (LiCoO) or other lithium-ion cells.
  • LiCoO lithium cobalt oxide
  • each of the first porous structure 316 and/or the second porous structure 326 may have a porosity based on one or more of a thermal, plasma, or combined thermal-plasma process using one or more of steam, hydrogen gas, carbon dioxide, oxygen, ozone, KOH, ZnC12, H3P04, or other similar chemical agents alone or in combination.
  • the macroporous pathways may have a principal dimension greater than 50 nm
  • the mesoporous pathways may have a principal dimension between approximately 20 nm and 50 nm
  • the microporous pathways may have a principal dimension less than 4 nm.
  • the macroporous pathways and mesoporous pathways can provide tunable conduits for transporting lithium ions 125, and the microporous pathways may confine active materials within the electrode 300.
  • the electrode 300 may include one or more additional thin films (not shown for simplicity).
  • Each of the one or more additional thin films may include individual aggregates interconnected with each other across different thin films, with at least some of the thin films having different concentration levels of aggregates.
  • the concentration levels of any thin film may be varied (such as by gradation) to achieve particular electrical resistance (or conductance) values.
  • the concentration levels of aggregates may progressively decline between the first thin film 310 and the last thin film (such as in a direction 195 depicted in Figure 1), and/or the individual thin films may have an average thickness between approximately 10 microns and approximately 200 microns.
  • the first thin film 310 may have a relatively high concentration of carbonaceous aggregates
  • the second thin film 320 may have a relatively low concentration of carbonaceous aggregates.
  • the relatively high concentration of aggregates corresponds to a relatively low electrical resistance
  • the relatively low concentration of aggregates corresponds to a relatively high electrical resistance.
  • the host structure 328 may be prepared with multiple active sites on exposed surfaces of the first aggregates 312 and/or the second aggregates 322. These active sites, as well as the exposed surfaces of the first aggregates 312 and/or the second aggregates 322, may facilitate ex-situ electrodeposition prior to incorporation of the electrode 300 into the battery 100. Electroplating is a process that can create a lithium layer 330 (including lithium on exposed surfaces of the host structure 328) through chemical reduction of metal cations by application and/or modulation of an electric current.
  • the host structure 328 may be electroplated such that the lithium layer 330 has a thickness between approximately 1 and 5 micrometers (pm), 5 pm and 20 pm, or greater than 20 pm. In some instances, ex-situ electrodeposition may be performed at a location separate from the battery 100 prior to the assembly of the battery 100.
  • excess lithium provided by the lithium layer 330 may increase the number of lithium ions 125 available for transport in the battery 100, thereby increasing the storage capacity, longevity, and performance of the battery 100 (as compared with traditional lithium-ion and/or lithium-sulfur batteries).
  • the lithium layer 330 may produce lithium-intercalated graphite (LiCe) and/or lithiated graphite based on chemical reactions with the first aggregates 312 and/or the second aggregates 322. Lithium intercalated between alternating graphene layers may migrate or be transported within the electrode 300 due to differences in electrochemical gradients during operational cycling of the battery 100, which in turn may increase the energy storage and power delivery of the battery 100.
  • LiCe lithium-intercalated graphite
  • lithiated graphite lithiated graphite
  • Lithium intercalated between alternating graphene layers may migrate or be transported within the electrode 300 due to differences in electrochemical gradients during operational cycling of the battery 100, which in turn may increase the energy storage and power delivery of the battery 100.
  • Figure 4 shows a diagram of a portion of an example battery 400 that includes a protective lattice 402, according to some implementations.
  • the protective lattice 402 may be disposed on the anode 220 of the battery 200.
  • the protective lattice 402 may be disposed on the cathode 210 of the battery 200 (or other suitable batteries).
  • the protective lattice 402 may be one example of the protective lattice 280 of Figure 2.
  • the protective lattice 402 may function with many components (e.g., anode, cathode, current collectors associated, carbonaceous materials, electrolyte, and separator) in a manner similar to the battery 100 of Figure 1 and/or the battery 200 of Figure 2.
  • components e.g., anode, cathode, current collectors associated, carbonaceous materials, electrolyte, and separator
  • the protective lattice 402 may include a tri-functional epoxy compound and a di amine oligomer-based compound that can chemically react with each other to produce a 3D lattice structure (e.g., as shown in Figure 6 and Figure 8).
  • the protective lattice 402 may prevent polysulfide migration within the battery 400 by providing nitrogen and oxygen atoms that can chemically bind with lithium present in the polysulfides, thereby impeding the migration of polysulfides through the electrolyte 130.
  • lithium ions 125 can be more freely transported from the anode 120 and the cathode 110 of Figure 1, thereby increasing battery performance metrics.
  • Cyclical usage of the cathode 110 may cause the formation of cracks 404 that at least partially extend into the cathode 110.
  • the protective lattice 402 may disperse throughout the cracks 404, thereby reducing susceptibility of the cathode 110 to rupture during volumetric expansion of the cathode 110 caused by the retention of polysulfides within the cathode 110 during cyclical usage.
  • the protective lattice 402 of Figure 4 may have a cross-linked, 3D structure based on chemical reactions between di-functional, or higher functionality Epoxy and Amine or Amide compounds..
  • the di-functional, or higher functionality Epoxy compound may be trimethylolpropane triglycidyl ether (TMPTE), tris(4-hydroxyphenyl)methane triglycidyl ether, or tris(2, 3 -epoxypropyl) isocyanurate, and di-functional, or higher functionality
  • Amine compound may be dihydrazide sulfoxide (DHSO) or one of polyetheramines, for example JEFF AMINE ® D-230 characterized by repeating oxypropylene units in the backbone.
  • DHSO dihydrazide sulfoxide
  • JEFF AMINE ® D-230 characterized by repeating oxypropylene units in the backbone.
  • the chemical compounds may be combined and reacted with each other in any number of quantities, amounts, ratios and/or compositions to achieve different performance capabilities relating to binding with poly sulfides generated during operation of the battery 400.
  • 113 mg of TMPTE and 134 mg of JEFF AMINE ® D-230 polyetheramine may be mixed together and diluted with 1 mL to 10 mL of tetrahydrofuran (THF), or any other solvent.
  • Additional amounts of TMPTE and/or JEFF AMINE may be mixed together and diluted in THF, or any other solvent, at an example ratio of 113 mg of TMPTE for every 134 mg of JEFF AMINE ® D- 230 polyetheramine.
  • proof-of-concept (POC) data shows that the protective lattice 402 of Figure 4 has a defined weight of approximately 2.6 wt.% of the cathode 110 of Figure 1 or the cathode 210 of Figure 2.
  • the protective lattice 402 may have a weight of approximately 2 wt.% to 21 wt. % of the cathode 110 and/or the cathode 210, where an impedance increases of the cathode 110 and/or the cathode 210 may be expected at a weight level of approximately 10 wt.% or more for the protective lattice 402.
  • the protective lattice 402 may be fabricated based on a mole and/or molar ratio of -N3 ⁇ 4 group and epoxy groups and may further accommodate various forms of cross-linking between di-functional, or higher functionality Epoxy and Amine or Amide compound.
  • forms of cross-linking may include a fully cross-linked stage, e.g., where one -N3 ⁇ 4 group is chemically bonded with two epoxy groups and may further extend to configurations including one N3 ⁇ 4 group chemically bonded with only one epoxy group.
  • mixtures including excess quantities (above the ratios presented here) of -Nth groups may be prepared to provide additional polysulfide binding capability for the protective lattice 402.
  • the protective lattice 402 may be prepared by mixing 201g of TMPTE with between 109g and 283g of JEFF AMINE ® D-230 polyetheramine. The resulting mixture may be then diluted with 1 L to 20 L of a selected solvent (such as THF). The resultant diluted solution may be deposited and/or otherwise disposed on the cathode 110 to achieve a crosslinker content between 1 wt.% to 10 wt.%. Additional TMPTE and/or JEFF AMINE may be mixed together and diluted in THF, or another suitable solvent, at an example ratio of 201g of TMPTE for every 109g to 283g of JEFF AMINE ® D-230 polyetheramine.
  • the protective lattice 402 may be prepared by mixing 201g of TMPTE with between 74g and 278g DHSO. The resulting mixture may be then diluted with 1 L to 20 L of a selected solvent (such as THF). The resultant diluted solution may be deposited and/or otherwise disposed on the cathode 110 to achieve a crosslinker content between 1 wt.% to 10 wt.%. Additional TMPTE and/or JEFF AMINE may be mixed together and diluted in THF, or another suitable solvent, at an example ratio of 201g of TMPTE for every 201g to 278g of JEFFAMINE ® D-230 polyetheramine.
  • di-functional, or higher functionality Epoxy compound may chemically react with di-functional, or higher functionality amine compound to produce the protective lattice 402 in a 3D cross-linked form, which may include both functional epoxy compounds and amine containing molecules.
  • the protective lattice 402 when deposited on the cathode 110 of Figure 1 or the cathode 210 of Figure 2, may have a thickness between approximately 1 nm and 5 pm.
  • the protective lattice 402 may increase the structural integrity of the cathode 110 or the cathode 210, may reduce surface roughness, and may retain polysulfides in the cathode.
  • the protective lattice 402 may serve as sheath on exposed surfaces of the cathode and bind with polysulfides to prevent their migration and diffusion into the electrolyte 130. In this way, aspects of the subject matter disclosed herein may prevent (or at least reduce) battery capacity decay by suppressing the polysulfide shuttle effect.
  • the protective lattice 402 may also fill the cracks 404 formed in the cathode of Figure 4 to improve cathode coating integrity.
  • the protective lattice 402 may be prepared by drop casting processes in the presence of a solvent, where the resultant solution can penetrate in cracks 404 of the cathode 110 and bind with poly sulfides in the cathode 110 to prevent their migration and/or diffusion throughout the electrolyte 130.
  • the protective lattice 402 may provide nitrogen atoms and/or oxygen atoms that can chemically bond with lithium in the polysulfides generated during operational battery cycling.
  • the polysulfides may bond with available nitrogen atoms provided by, for example, DHSO.
  • the polysulfides may bond with available oxygen atoms provided by, for example, DHSO.
  • the poly sulfides may bond with other available oxygen atoms.
  • the recipes described above may be altered by replacing TMPTE with a tris(4-hydroxyphenyl)methane triglycidyl ether 910 and/or a tris(2, 3 -epoxypropyl) isocyanurate.
  • the di-amine oligomer-based compound may be (or may include) a JEFF AMINE ® D-230, or other polyetheramines containing polyether backbone normally based on either propylene oxide (PO), ethylene oxide (EO), or mixed PO/EO structure, for example JEFF AMINE ® D-400, JEFF AMINE ® T-403.
  • the protective lattice 402 may also include various concentration levels of inert molecules, e.g., polyethylene glycol chains of various lengths, which may allow to fine-tune mechanical properties of protective lattice and the chemical bonding of various atoms to lithium present in the poly sulfides.
  • inert molecules e.g., polyethylene glycol chains of various lengths
  • FIG. 5 shows a diagram of an anode structure 500 that includes a tin fluoride (SnF2) layer, according to some implementations.
  • the diagram depicts a cut away schematic view of the anode structure 500 in which all of the components associated with a first region A have identical counterparts in a second region B, where the first and second regions A and B have opposite orientations around a current collector 520.
  • the description below with reference to the components of first region A is equally applicable to the components of second region B.
  • the anode 502 may be one example of the anode 120 of Figure 1 and/or the anode 220 of Figure 2.
  • lithium- sulfur batteries such as the battery 100 of Figure 1 and the battery 200 of Figure 2, operate as conversion-chemistry type electrochemical cells in that sulfur pre-loaded into the cathode may dissolve rapidly into the electrolyte prior to and during operation.
  • Lithium which may be provided by lithiated anodes and/or may be prevalent in the electrolyte, dissociates into lithium ions (Li+) suitable for transport from the anode to the cathode through the electrolyte.
  • the production of lithium ions is associated with a corresponding release of electrons, which may flow through an external circuit to power a load, as described with reference to Figure 1.
  • lithium when lithium disassociates into lithium ions and electrons, some of the lithium ions may undesirably react with polysulfides produced in the cathode, and therefore may no longer be available to generate an output current or voltage.
  • This consumption of lithium ions by polysulfides reduces the overall capacity of the host cell or battery, and may also facilitate corrosion of the anode, which can result in cell failure.
  • the protective layer 516 may be provided as passivation coating that can reduce the chemical reactivity of the anode 502 during cell assembly or formation.
  • the protective layer 516 may be permeable to lithium ions while concurrently protecting the anode 502 from corrosion caused by chemical reactions between lithium ions and polysulfides.
  • the protective layer 516 may be an artificial solid-electrolyte interphase (A-SEI) that can replace naturally occurring SEIs and/or other types of conventional A-SEIs.
  • the protective layer 516 may be deposited as a liner on top of one or more films disposed on the anode 502.
  • the protective layer 516 may be a self-generating layer that forms during electrochemical reactions associated with operational cycling of the battery. In some aspects, the protective layer 516 may have a thickness that is less than 5 microns. In other aspects, the protective layer 516 may have a thickness between 0.1 and 1.0 microns.
  • one or more engineered additives that may facilitate the formation and/or deposition of the protective layer 516 on the anode 502 may be provided within the electrolyte of the battery.
  • the engineered additives may be an active ingredient of the protective layer 516.
  • the protective layer 516 may provide tin ions and/or fluoride ions that can prevent undesirable lithium growths from a first edge 518 1 and a second edge 518 2 of the anode.
  • a graded layer 514 may be formed and/or deposited onto the anode 502 beneath the protective layer 516.
  • the graded layer 514 may prevent lithium contained in or associated with the anode 502 from participating in undesirable chemical interactions and/or reactions with the electrolyte 540 that can lead to the growth of lithium-containing dendrites from the anode 502.
  • the graded layer 514 may also facilitate the production of lithium fluoride based on chemical reactions between dissociated lithium ions and fluoride ions. As discussed, the presence of lithium fluoride in or near the anode 502 can decrease the polysulfide shuttle effect.
  • lithium fluoride e.g., form available lithium ions and fluorine ions
  • formation of lithium fluoride may occur uniformly across the entirety of the first edge 518i and/or the second edge 5182 of the anode.
  • localized regions of high lithium concentration in the electrolyte 540 near the anode 502 are substantially inhibited.
  • lithium-lithium bonds contributing to the formation of lithium containing dendritic structures extending length-wise from the anode are correspondingly inhibited, thereby yielding free passage of lithium ions from the anode 502 into the electrolyte (e.g., as encountered during battery operational cycling).
  • the uniform distribution of lithium throughout the graded layer 514 can increase a uniformity of a lithium-ion flux during battery operational cycling.
  • the graded layer 514 may be approximately 5 nanometers (nm) in thickness.
  • the graded layer 514 may structurally reinforce the host battery in a manner that not only decreases or prevents lithium-containing dendritic growth from the anode 502 but also increases the ability of the anode 502 to expand and contract during operational cycling of the host battery without rupturing.
  • the graded layer 514 has a 3D architecture with a graded concentration gradient (e.g., of one or more formative materials and/or ingredients including carbon, tin, and/or fluorine), which facilitates rapid lithium-ion transport. As a result, the graded layer 514 markedly improves overall battery efficiency and performance.
  • the graded layer 514 may provide an electrochemically desirable surface upon which the protective layer 516 may be grown or deposited.
  • the graded layer 514 may include compounds and/or organometallic compounds including (but not limited to) aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and/or other metals.
  • the graded layer 514 may include oxides, carbides and/or nitrides of aluminum, gallium, indium, nickel, zinc, chromium, vanadium, titanium, and/or other metals.
  • the graded layer 514 may include carbonaceous materials including (but not limited to) flaky graphene, few layer graphene (FLG), carbon nano onions (CNOs), graphene nanoplatelets, or carbon nanotubes (CNTs).
  • the graded layer 514 may include carbon, oxygen, hydrogen, tin, fluorine and/or other suitable chemical compounds and/or molecules derived from tin fluoride and one or more carbonaceous materials.
  • the graded layer 514 may be prepared and/or deposited either directly or indirectly on the anode 502 at a different concentration levels.
  • the graded layer 514 may include 5 wt. % carbonaceous materials with a balance of 95 wt. % tin fluoride, which may result in a relatively uniform disassociation of fluorine atoms and/or fluoride ions from the tin fluoride.
  • Suitable ratios include: 5% carbonaceous materials with 95% tin fluoride; 10% carbonaceous materials with 90% tin fluoride, 15% carbonaceous materials with 85% tin fluoride, 20% carbonaceous materials with 80% tin fluoride, 25% carbonaceous materials with 75% tin fluoride, 30% carbonaceous materials with 70% tin fluoride, 35% carbonaceous materials with 65% tin fluoride, 40% carbonaceous materials with 60% tin fluoride, 45% carbonaceous materials with 55% tin fluoride, 50% carbonaceous materials with 50% tin fluoride, 55% carbonaceous materials with 45% tin fluoride, 55% carbonaceous materials with 45% tin fluoride, 60% carbonaceous materials with 40% tin fluoride, 65% carbonaceous materials with 35% tin fluoride, 70% carbonaceous materials with 30% tin fluoride, 75% carbonaceous materials with 25% tin fluoride, 80% carbonaceous
  • lithium ions cycling between the anode 502 and the cathode may produce a tin-lithium alloy region 512 within the graded layer 514.
  • operational cycling of the host battery may result in a uniform dispersion of lithium fluoride within the tin-lithium alloy region 512.
  • the uniform dispersion of lithium fluoride may facilitate a defluorination reaction of at least some of tin (II) fluoride (SnF 2) within the tin fluoride layer 510 (and additional tin fluoride which may have dispersed into the graded layer 514 and/or the protective layer).
  • the fluorine atoms and/or fluoride ions made available by the defluorination reaction may chemically bond with at least some of the lithium ions present in or near the anode 502, to create lithium fluoride (LiF) and correspondingly thereby prevent at least some of the lithium ions from bonding with each other and creating a lithium dendritic growth from the anode 502.
  • LiF lithium fluoride
  • the fluorine atoms and/or fluoride ions present in the tin fluoride may dissociate from the protective layer 516 and produce tin ions (Sn 2+ ) and fluorine ions (2F ) via one or more chemical reactions.
  • the fluorine atoms and/or fluoride ions dissociated from the protective layer 516 may chemically bond to at least some of the lithium ions present in the electrolyte 540 and/or dispersed throughout the protective layer 516 or the graded layer 514.
  • the dissociated fluorine atoms may form Li — F bonds or Li — F compounds in the tin-lithium alloy region 512.
  • the dissociated fluorine atoms may form a tin fluoride layer 510 within the graded layer 514.
  • the defluorinated tin fluoride may disperse uniformly throughout the graded layer 514 to produce lithium fluoride (LiF) crystals.
  • the lithium fluoride crystals may act as an electrical insulator and prevent the flow of electrons from the anode 502 into the electrolyte 540 through the first edge 518i and/or the second edge 518 2 of the anode 502.
  • the graded layer 514 may be deposited on the anode 502 by one or more of atomic layer deposition (ALD), chemical vapor deposition (CVD), or physical vapor deposition (PVD).
  • ALD may be used to deposit protective films on the anode 502 such as, for example, an ALD film that at least partially reacts with the electrolyte 540 during high-pressure bonding processes.
  • the ALD film may be used to produce the protective layer 516 or the graded layer 514 using an atomic plane available for lithium transfer.
  • Such lithium transfer may be similar in principle to that observed for few layer graphene (FLG) or graphite, where alternating graphene layers in FLG or graphite intercalate lithium ions in various forms including as lithium titanium oxide (LTO), lithium iron phosphate (PO3) (LFP).
  • LTO lithium titanium oxide
  • PO3 lithium iron phosphate
  • the described forms of intercalated lithium, e.g., LTO and/or LFP may be oriented to facilitate rapid lithium atom and/or lithium ion transport and/or diffusion, which may be conducive for the formation and/or synthesis of lithium fluoride (e.g., in the tin fluoride layer 510 and/or elsewhere), as described earlier.
  • Additional forms of intercalated lithium e.g., perovskite lithium lanthanum titanate (LLTO), may also function to store lithium within the anode 502.
  • the graded layer 514 may include various distinct types and/or forms of carbon and/or carbonaceous materials, each having one or more physical attributes that can be selected or configured to adjust the reactivity of carbon with contaminants (such as polysulfides) present in the electrolyte 540 and/or the anode 502.
  • the selectable physical attributes may include (but are not limited to) porosity, surface area, surface functionalization, or electric conductivity.
  • the graded layer 514 may include binders or other additives that can be used to adjust one or more physical attributes of the carbonaceous materials to achieve a desired reactivity of carbon supplied by the carbonaceous materials with polysulfides present in the electrolyte 540 and/or the anode 502.
  • carbonaceous materials within the graded layer 514 may capture unwanted contaminants and thereby prevent the contaminants from chemically reacting with lithium available at exposed surfaces of the anode 502. Instead, the unwanted contaminants (e.g., polysulfides) may chemically react with various exposed surfaces of the carbonaceous materials within the graded layer 514 (e.g., through carbon - lithium interactions). In some implementations, the carbonaceous materials within the graded layer 514 may cohere to the available lithium. The degree of cohesion between the carbonaceous materials and the lithium ions may be selected or modified via chemical reactions induced during preparation of the graded layer 514.
  • the unwanted contaminants e.g., polysulfides
  • the carbonaceous materials within the graded layer 514 may cohere to the available lithium. The degree of cohesion between the carbonaceous materials and the lithium ions may be selected or modified via chemical reactions induced during preparation of the graded layer 514.
  • various carbon allotropes may be incorporated within the graded layer 514 (such as in one or more portions of the tin-lithium alloy region 512 and/or the tin fluoride layer 510). These carbon allotropes may be functionalized with one or more reactants and used to form a sealant layer and/or region at an interface of carbon nanodiamonds within the graded layer 514 and the electrolyte 540. In some aspects, the carbon nanodiamonds may increase the mechanical robustness of the anode 502 and/or the graded layer 514.
  • the carbon nanodiamonds may also provide exposed carbonaceous surfaces that may be used to decrease the polysulfide shuttle effect by micro- confining and/or bonding with polysulfides present in the electrolyte 540 in a manner that retains the polysulfides within defined regions of the battery external to the anode 502.
  • the carbon nanodiamonds within the graded layer 514 may be replaced with carbons and/or carbonaceous materials including surfaces and/or regions having a specific LA dimensions (e.g., sp 2 hybridized carbon), reduced graphene oxide (rGO), and/or graphene.
  • employing the carbonaceous materials disclosed herein within a battery may increase carbon stacking and layer formation within the graded layer 514. Exfoliated and oxidized carbonaceous materials may also yield more uniform layered structures within the graded layer 514 (as compared to carbonaceous materials that have not been exfoliated and oxidized).
  • solvents such as tetrabutylammonium hydroxide (TBA) and/or dimethyl formamide (DMF) treatments may be applied to the carbonaceous materials disclosed herein to increase the wetting of exposed carbonaceous surfaces within the graded layer 514.
  • TSA tetrabutylammonium hydroxide
  • DMF dimethyl formamide
  • slurries used to form the graded layer 514 may be doped to improve or otherwise influence the crystalline structure of carbonaceous materials within the graded layer 514.
  • addition of certain dopants may influence the crystalline structure of the carbonaceous materials in a certain corresponding way, and functional groups may be added (e.g., via grafting onto exposed carbon atoms within the carbonaceous materials) within the graded layer 514.
  • carbonaceous materials having exposed surfaces functionalized with one or more of fluorine-containing or silicon-containing functional groups may be included within the graded layer 514.
  • carbonaceous materials having exposed surfaces functionalized with one or more of fluorine-containing or silicon-containing functional groups may be deposited beneath the graded layer 514 to form a stable SEI on at an interface between the graded layer 514 and the anode 502.
  • the stable SEI may replace the protective layer 516.
  • the graded layer 514 may be slurry cast and/or deposited using other techniques onto the anode 502 with lithium and carbon interphases, any of which may be functionalized with silicon and/or nitrogen to inhibit the diffusion and migration of polysulfides towards exposed surfaces of the anode 502.
  • specific polymers and/or crosslinkers may be incorporated within the graded layer 514 to mechanically strengthen the graded layer 514, to improve lithium ion transport across the graded layer 514, or to increase the uniformity of lithium ion flux across the graded layer 514.
  • Example polymers and/or polymeric materials suitable for incorporation within the graded layer 514 may include poly(ethylene oxide) and poly(ethyleneimine).
  • Example crosslinkers suitable for incorporation within the graded layer 514 may include inorganic linkers (e.g., borate, aluminate, silicate), multifunctional organic molecules (e.g., diamines, diols), polyurea, or high molecular weight (MW) (e.g., >10,000 daltons) carboxymethyl cellulose (CMC).
  • inorganic linkers e.g., borate, aluminate, silicate
  • multifunctional organic molecules e.g., diamines, diols
  • polyurea e.g., polyurea
  • MW high molecular weight
  • CMC carboxymethyl cellulose
  • direct coating of the interface between the anode 502 and the electrolyte 540 prior to the deposition and/or formation of the graded layer 514 may be performed with a dispersion of carbonaceous materials and other chemicals dissolved in a carrier (e.g., a solvent, binder, polymer).
  • a carrier e.g., a solvent, binder, polymer
  • deposition of the graded layer 514 may be performed as a separate operation, or may be added to various other active ingredients (e.g., metals, carbonaceous materials, tin fluoride and/or the like) into a slurry that can be cast onto the anode 502.
  • the protective layer 516 may be transferred directly onto the anode 502 by a calendar roll lamination processes.
  • the protective layer 516 and/or the graded layer 514 may also incorporate partially-cured lithium ion conductive epoxies to, for example, increase adhesion with lithium better during the calendar roll lamination processes.
  • a carbon-inclusive layered structure (not shown in Figure 5) may be disposed on the anode 502 as a replacement for the graded layer 514.
  • the carbon- inclusive layered structure may include an atomic plane available for lithium transfer, and may uniformly transport lithium ions provided by the electrolyte 540 throughout the protective layer 516 in a manner that can guide the formation of lithium fluoride in various portions of the battery.
  • the carbon-inclusive layered structure may include one or more arrangements of few layer graphene (FLG) or graphite and/or may intercalate with lithium and produce one or more reaction products including lithium tin oxide (LTO), lithium iron phosphate (LFP), or perovskite lithium lanthanum titanate (LLTO).
  • FLG few layer graphene
  • LTO lithium tin oxide
  • LFP lithium iron phosphate
  • LLTO perovskite lithium lanthanum titanate
  • the tin fluoride layer 510 may function as a protection layer against corrosion, including corrosion of copper-inclusive surfaces and/or regions of the protective layer 516, the graded layer 514, or the anode 502. In some aspects, the tin fluoride layer 510 may also provide a uniform seed layer suitable for lithium deposition, and thereby inhibiting dendrite formation. In addition, in some implementations, the tin fluoride layer 510 may include one or more lithium ion intercalating compounds, any one or more having a low voltage penalty. Suitable lithium ion intercalating compounds may include graphitic carbon (e.g., graphite, graphene, reduced graphene oxide, rGO).
  • graphitic carbon e.g., graphite, graphene, reduced graphene oxide, rGO
  • lithium ions may tend to intercalate prior to plating onto exposed carbonaceous surfaces within the tin fluoride layer 510.
  • the tin fluoride layer 510 will have a uniform Li distribution ready to act as a seed layer prior to initiation of lithium plating and/or electroplating operations.
  • one or more conformal coatings may be applied over portions of the anode 502 such that the resulting conformal coating contacts and conforms to the first edge 518i and/or the second edge 518 2 of the anode 502.
  • the conformal coating may begin as a first spacer edge protection region 530i and a second spacer edge protection region 530 2 that react or otherwise combine with one or more of the protective layer 516, the tin-lithium alloy region 512, and/or the tin fluoride layer 510 to form a conformal coating 544 that at least partially seals and protects surfaces and/or interfaces between lithium in the anode 502 and various substances suspended in the electrolyte, e.g., copper (Cu).
  • Cu copper
  • the dissociation of fluorine atoms from tin fluoride present in the conformal coating 544 may react with lithium in the anode 502 to form lithium fluoride, rather than form or grow into lithium dendrites. In this way, the conformal coating 544 may decrease lithium dendrite formation or growth from the anode 502.
  • the conformal coating 544 may be deposited or disposed over the anode 502 at any number of different thicknesses. In some aspects, the conformal coating 544 may be less than 5 pm thick. In other aspects, the conformal coating 544 may be less than 2 pm thick. In some other aspects, the conformal coating 544 may be less than 1pm thick.
  • These thickness levels may impede the migration of poly sulfides towards the anode 502 during battery cycling, thereby preventing at least some of the lithium ions from reacting with the polysulfides. Lithium ions that do not react with the polysulfides are available for transport from the anode to the cathode during discharge cycles of the battery.
  • the conformal coating 544 (as well as the protective layer 516 and the graded layer 514) can uniquely regulate lithium ion flux toward the first edge 518i and/or the second edge 5182 of the anode 502, and thereby prevent corrosion of the anode 502.
  • Such regulation may function in a similar manner to gate spacers used during the fabrication of polysilicon (poly-Si) gates.
  • gate spacer or gate sidewall constructs may be used to protect and mechanically support polysilicon gates during the fabrication of integrated circuits (ICs).
  • edge protection provided by the conformal coating 544 for the anode 502 of Figure 5 regulates lithium ion flux toward the first edge 5181 and/or the second edge 5182 of the anode 502, and thereby prevents corrosion of the anode 502.
  • This type of edge protection provided by the conformal coating 544 for the anode 502 may equally apply to other battery and/or electrical cell formats and/or configurations such as (but not limited to) cylindrical cells, stacked cells, and/or the like, with various constructs engineered specifically to fit within the parameters of each of these designs.
  • fabrication and/or deposition of the conformal coating 544, the protective layer 516, and/or the graded layer 514 on the anode 502 may depend on the type of battery or cell construct in which the anode 502 is incorporated, e.g., cylindrical cells compared to pouch cells and/or prismatic cells.
  • metal anodes may be constructed from an electroactive material, typically metallic lithium, and/or lithium-containing alloys, such as graphitic and/or other carbonaceous composited including lithium, as well as any plenary uniform or multi-layer sheet of material.
  • a solid metal lithium foil used as the anode 502 may be attached to a copper substrate used as the current collector 520 to facilitate electron transfer through a tab 546 to an external load, as depicted in the example of Figure 5.
  • the battery 500 may include the anode 502 without the current collector 520, where carbonaceous materials contained within the anode 502 may provide an electrically conductive medium coupled to a circuit.
  • the anode structure 500 may be incorporated into electrochemical cells and/or batteries by winding around a mandrel. Cylindrical cell layouts typically use double-sided anodes, such as the anode structure 500. In some implementations, cylindrical cell constructions employing the anode structure 500 may use the conformal coating 544 to protect the first edge 518 1 and/or the second edge 518 2 of the anode 502.
  • edge protection The uniform protection provided by the conformal coating 544 may be referred to herein as “edge protection.”
  • edge protection can be incorporated into a cell employing the anode structure 500 by extending the size and/or area of the protective layer 516 to overlap beyond any geometrically induced edge effects, e.g., surface roughness, of the anode.
  • the anode stmcture 500 may be incorporated into pouch cells and/or prismatic cells.
  • two constructs of pouch and/or prismatic cells may be manufactured, including (1): jelly-roll type cells (e.g., seen in industry as lithium-polymer batteries), two mandrel wound electrodes may be produced in a manner similar to cylindrical cells as discussed earlier; and (2): stacked plate type cells, which may be cut from a sheet of a pre-cast and/or pre-laminated prepared anode, leaving an unprotected edge of, for example, the anode 502 (when prepared in a stacked-plate type configuration) exposed and vulnerable to corrosion, fast ion fluxes and exposure within the cells.
  • jelly-roll type cells e.g., seen in industry as lithium-polymer batteries
  • two mandrel wound electrodes may be produced in a manner similar to cylindrical cells as discussed earlier
  • stacked plate type cells which may be cut from a sheet of a pre-cast and/or pre-laminated prepared an
  • the conformal coating 544 in a stacked-plate type configuration, may protect the anode 502 and prevent lithium over saturation in the electrolyte 540. In this way, the conformal coating 544 can control lithium plating on the anode 502 during operational cycling of the battery.
  • one or more chemical reactions may occur between the electrolyte 540 and the anode 502 (involving solvent decomposition and/or additive reactions) during cell assembly or cell rest period. These chemical reactions may assist in the production of the conformal coating 544.
  • elevated and/or reduced temperatures e.g., relative to room temperature and/or 20°C
  • the lithium- induced polymerization may occur in the presence of one or more catalysts and/or by using lithium metal, and its associated chemical reactivity, as an inducing agent to initiate free- radical based polymerization of constituent species within any one or more layers of the anode stmcture 500 and/or the conformal coating 544.
  • electrochemical reactions under electrical bias in either the forward or reverse direction may be used to fabricate and/or deposit the conformal coating 544 onto the anode 502, as well as usage of secondary metals and/or salts as additives that may decompose to form an alloy on the first edge 518i and/or the second edge 518 2 of metallic lithium in the anode 502 exposed to the electrolyte 540.
  • suitable additives may contain one or more metallic species, e.g., desired for co alloying with lithium or to be used as a blocking layer to reduce lithium transfer to the first edge 518i and/or the second edge 518 2 of the anode 502.
  • FIG. 6 shows a schematic diagram of an enlarged portion 600 of the anode structure 500 of Figure 5, according to some implementations.
  • the enlarged portion 600 illustrates placement of the first spacer edge protection region 530i and the second spacer edge protection region 530 2 (collectively referred to as the edge protection region 530 in Figure 6) in a direction orthogonal to the first edge 518i and/or the second edge 518 2 , as shown in Figure 5.
  • the edge protection region 530 which may include the carbonaceous materials 610 organized into structures and/or lattices, may block lithium ions from undesirably escaping the anode 502 across the edge protection region 530.
  • carbonaceous materials 610 used to produce the edge protection region may include few layer graphene (FLG), multi-layer graphene (MLG), graphite, carbon nano-tubes (CNTs), carbon nano-onions (CNOs) and/or the like.
  • the carbonaceous materials 610 may be synthesized, self-nucleated, or otherwise joined together at varying concentration levels to provide for complete tunability of the edge protection region 530.
  • the density, thickness, and/or compositions of may be designed to reduce lithium ion permeation more than the protective layer 516 or the graded layer 514 to direct lithium ion permeation accordingly.
  • the edge protection region 530 may be less than 5 pm thick. In other aspects, the edge protection region 530 may be less than 2 pm thick. In some other aspects, the edge protection region 530 may be less than 1pm thick.
  • a conductive additive 640 may be added to the carbonaceous materials 610, as well as a binder 620.
  • Figure 7 shows a diagram of a polymeric network 710, according to some implementations.
  • the polymeric network 710 may be one example of the polymeric network 285 of Figure 2.
  • the polymeric network 710 may be disposed on an anode 702.
  • the anode 702 may be formed as an alkali metal layer having one or more exposed surfaces that include any number of alkali metal-containing nanostructures or microstructures.
  • the alkali metal may include (but is not limited to) lithium, sodium, zinc, indium and/or gallium.
  • the anode 702 may release alkali ions during operational cycling of the battery.
  • a layer 714 of carbonaceous materials may be grafted with fluorinated polymer chains and deposited over one or more exposed surfaces of the anode 702.
  • the grafting may be based on (e.g., initiated by) activation of carbonaceous material with one or more radical initiators, for example, benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN), followed by reaction with monomer molecules.
  • BPO benzoyl peroxide
  • AIBN azobisisobutyronitrile
  • the polymeric network 710 may be based on the fluorinated polymer chains cross-linked with one another and carbonaceous materials of the layer 714 such that the layer 714 is consumed during generation of the polymeric network 710.
  • the polymeric network 710 may have a thickness approximately between 0.001 pm and 5 pm and include between approximately 0.001 wt.% to 2 wt.% of the fluorinated polymer chains. In some other implementations, the polymeric network 710 may include between approximately 5 wt.% to 100 wt.% of the plurality of carbonaceous materials grafted with fluorinated polymer chains and a balance of fluorinated polymers, or one or more non-fluorinated polymers, or one or more cross-linkable monomers, or combinations thereof. In one implementation, carbonaceous materials grafted with fluorinated polymer chains may include 5 wt.% to 50 wt.% of fluorinated polymer chains and a balance of carbonaceous material.
  • carbon-fluorine bonds within the polymeric network 710 may chemically react with newly forming Lithium metal and convert into carbon-Lithium bonds (C-Li). These C-Li bonds may, in turn, react with carbon-fluorine bonds within the polymeric network 710 via a Wurtz reaction 750, to further cross-link polymeric network by newly formed C-C bonds and to form an alkali-metal containing fluoride (such as lithium fluoride (LiF)). Additional polymeric network cross-linking leading to uniform formation of the alkali-metal containing fluoride may thereby suppress alkali metal dendrite formation 740 associated with the anode 702, thereby improving battery performance and longevity.
  • C-Li carbon-Lithium bonds
  • grafting of fluorinated m/acrylate (FMA) to one or more exposed graphene surfaces of carbonaceous materials in the layer 714 may be performed in an organic solution, e.g., leading to the formation of graphene-graft-poly-FMA and/or the like.
  • Incorporation of carbon-fluorine bonds on exposed graphene surfaces may enable the Wurtz reaction 750 to occur between carbon-fluorine bonds and metallic surface of an alkali metal (e.g., lithium) provided by the anode 702.
  • an alkali metal e.g., lithium
  • completion of the Wurtz reaction 750 may result in the formation of the polymeric network 710.
  • the polymeric network 710 may include a density gradient 716 pursuant to completion of the Wurtz reaction 750.
  • the density gradient 716 may include interconnected graphene flakes and may be infused with one or more metal-fluoride salts formed in-situ.
  • layer porosity and/or mechanical properties may be tuned by carbon loading and/or a combination of functionalized carbons, each having a unique and/or distinct physical structure.
  • carbonaceous materials within the density gradient 716 may include one or more of flat graphene, wrinkled graphene, a plurality of carbon nano tubes (CNTs), or a plurality of carbon nano-onions (CNOs) (e.g., as depicted in Figure 8A and/ Figure 8B and as shown in the micrographs of Figures 9A-9B and Figures 10A-10B).
  • graphene nanoplatelets may be dispersed throughout and isolated from each other within the polymeric network 710. The dispersion of the graphene nanoplatelets includes one or more different concentration levels.
  • the dispersion of the graphene nanoplatelets may include at least some of the carbonaceous materials functionalized with at least some of the fluorinated polymer chains.
  • the fluorinated polymer chains may include one or more acrylate or methacrylate monomers including 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl acrylate (DFHA), 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate (HDFDMA), 2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate (OFPMA), Tetrafluoropropyl methacrylate (TFPM), 3-[3,3,3-Trifluoro-2-hydroxy-2-
  • DFHA 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl acrylate
  • HDFDMA 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate
  • OFFPMA 2,2,3,3,4,4,5,5-Octa
  • HFA monomer 2,3,4,5,6-Pentafluorostyrene (PFSt).
  • PFSt 2,3,4,5,6-Pentafluorostyrene
  • fluorinated polymer chains may be grafted to a surface of the layer of carbonaceous materials and may thereby chemically interact with the one or more surfaces of the alkali metal of the anode via the Wurtz reaction 750.
  • the Wurtz reaction is a coupling reaction, whereby two alkyl halides are reacted with sodium metal (or some other metal) in dry ether solution to form a higher alkane.
  • alkyl halides are treated with alkali metal, for example, sodium metal in dry ethereal (free from moisture) solution to produce higher alkanes.
  • the polymeric network 710 may include an interface layer 718 in contact with the anode 702.
  • a protective layer 720 may be disposed on top of the interface layer 718, which may be based on the Wurtz reaction 750 at an interface between the anode 702 and the polymeric network 710.
  • the interface layer 718 may have a relatively high cross-linking density (e.g., of fluorinated polymers and/or the like), a high metal- fluoride concentration, and a relatively low carbon-fluorine bond concentration.
  • the protective layer 720 may have a relatively low cross-linking density, a low metal-fluoride concentration, and a high carbon-fluorine bond concentration.
  • the interface layer 718 may include cross-linkable monomers such as methacrylate (MA), acrylate, vinyl functional groups, or a combination of epoxy and amine functional groups.
  • the protective layer 720 may be characterized by the density gradient 716. In this way, the density gradient 716 may be associated with one or more self-healing properties of the protective layer 720 and/or may strengthen the polymeric network 710. In some implementations, the protective layer 720 may further suppress alkali metal dendrite formation 740 from the anode 702 during battery cycling.
  • the interface layer 718 may suppress alkali metal dendrite formation 740 associated with the anode 702 by uniformly producing metal-fluorides, e.g., lithium fluoride, at an interface across the length of the anode 702.
  • metal-fluorides e.g., lithium fluoride
  • the uniform production of metal fluorides causes dendrite surface dissolution, e.g., via conversion into metal- fluorides, ultimately suppressing alkali metal dendrite formation 740.
  • cross- linking of fluorinated polymer chains over remaining dendrites may further suppress alkali metal dendrite formation 740.
  • the density gradient 716 may be tuned to control the degree of cross-linking between the fluorinated polymer chains.
  • FIG 8A shows a simplified cutaway view of an example carbonaceous particle 800 with graded porosity, according to some implementations.
  • the carbonaceous particle 800 may be synthesized in a reactor, and output in a controlled manner to produce the cathode 110 and/or anode 120 of Figure 1, the cathode 210 and/or anode 220 of Figure 2, or the electrode 300 of Figure 3.
  • the carbonaceous particle 800 which may also be referred to as a composition of matter, includes a plurality of regions nested within each other. Each region may include at least a first porosity region 811 and a second porosity region 812.
  • the first porosity region 811 may include a plurality of first pores 801, and the second porosity region 812 may include a plurality of second pores 802. In some aspects, each region may be separated from immediate adjacent regions by at least some of the first pores 801.
  • the first pores 801 may be dispersed throughout the first porosity region 811 of the carbonaceous particle 800, and the second pores 802 may be dispersed throughout the second porosity region 812 of the carbonaceous particle 800. In this way, the first pores 801 may be associated with a first pore density, and the second pores 802 may be associated with a second pore density that is different than the first pore density.
  • the first pore density may be between approximately 0.0 cubic centimeters (cc)/g and 2.0 cc/g, and the second pore density may be between approximately 1.5 and 5.0 cc/g.
  • the first pores 801 may be configured to retain poly sulfides 820, and the second pores 802 may provide exit pathways from the carbonaceous particle 800.
  • a group of carbonaceous particles 800 may be joined together to form a carbonaceous aggregate (not shown for simplicity), and a group of carbonaceous aggregates may be joined together to form a carbonaceous agglomerate (not shown for simplicity).
  • the first pores 801 and second pores 802 may be dispersed throughout aggregates formed by respective groups of the carbonaceous particles 800.
  • the first porosity region 811 may be at least partially encapsulated by the second porosity region 812 such that a respective agglomerate may include some of the first pores 801 and/or some of the second pores 802.
  • the carbonaceous particle 800 may have a principal dimension “A” in an approximate range between 20 nm and 150 nm, an aggregate formed by a group of the carbonaceous particle 800 may have a principal dimension in an approximate range between 20 nm and 10 pm, and an agglomerate formed by a group of aggregates may have a principal dimension in an approximate range between 0.1 pm and 1,000 pm.
  • at least some of the first pores 801 and the second pores 802 has a principal dimension in an approximate range between 1.3 nm and 32.3 nm.
  • each of the first pores 801 has a principal dimension in an approximate range between 0 nm and 100 nm.
  • the carbonaceous particle 800 may also include a plurality of deformable regions 813 distributed along a perimeter 810 of the carbonaceous particle 800.
  • the carbonaceous particle 800 may conduct electricity along joined boundaries with (such as the perimeter 810) one or more other carbonaceous particles.
  • the carbonaceous particle 800 may also confine poly sulfides 820 within the first pores 801 and/or at one or more blocking regions 822, thereby inhibiting the migration of poly sulfides 820 towards the anode and increasing the rate at which lithium ions can be transported from the anode to the cathode of a host battery.
  • the carbonaceous particle 800 may have a surface area of exposed carbon surfaces in an approximate range between 10 m 2 /g to 3,000 m 2 /g. In other implementations, the carbonaceous particle 800 may have a composite surface area including sulfur 824 micro-confined within a number of the first pores 801 and/or a number of the second pores 802.
  • the first pores 801 and/or the second pores 802 that micro confine the polysulfides 820 may be referred to as “functional pores.”
  • one or more of the carbonaceous particles, the aggregates formed by corresponding groups of carbonaceous particles, or the agglomerates formed by corresponding groups of aggregates may include one or more exposed carbon surfaces configured to nucleate the sulfur 824.
  • the composite surface area may be in an approximate range between 10 m 2 /g to 3,000 m 2 /g, and the carbonaceous particle 800 may have a sulfur to carbon weight ratio between approximately 1:5 to 10:1.
  • the carbonaceous particle 800 may have an electrical conductivity in an approximate range between 100 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi).
  • the carbonaceous particle 800 may include a surfactant or a polymer that includes one or more of styrene butadiene rubber, polyvinylidene fluoride, poly acrylic acid, carboxyl methyl cellulose, polyvinylpyrrolidone, and/or polyvinyl acetate that can act as a binder to join a group of the carbonaceous particles 800 together.
  • the carbonaceous particle 800 may include a gel-phase electrolyte or a solid-phase electrolyte disposed within at least some of the first pores 801 or second pores 802.
  • FIG 8B shows a diagram of an example of a tri-zone particle 850, according to some implementations.
  • the tri-zone particle 850 may be one example of the carbonaceous particle 800 of Figure 8A.
  • the tri-zone particle 850 may include three discrete zones such as (but not limited to) a first zone 851, a second zone 852, and a third zone 853.
  • each of the zones 851-853 surrounds and/or encapsulates a preceding zone.
  • the first zone 851 may be surrounded by or encapsulated by the second zone 852
  • the second zone 852 may be surrounded by or encapsulated by the third zone 853.
  • the first zone 851 may correspond to an inner region of the tri-zone particle 850
  • the second zone 852 may correspond to an intermediate transition region of the tri-zone particle 850
  • the third zone 853 may correspond to an outer region of the tri-zone particle 850.
  • the tri-zone particle 850 may include a permeable shell 855 that deforms in response to contact with one or more adjacent non-tri- zone particles and/or tri-zone particles 850.
  • the first zone 851 may have a relatively low density, a relatively low electrical conductivity, and a relatively high porosity
  • the second zone 852 may have an intermediate density, an intermediate electrical conductivity, and an intermediate porosity
  • the third zone 853 may have a relatively high density, a relatively high electrical conductivity, and a relatively low porosity.
  • the first zone 851 may have a density of carbonaceous material between approximately 1.5 g/cc and 5.0 g/cc
  • the second zone 852 may have a density of carbonaceous material between approximately 0.5 g/cc and 3.0 g/cc
  • the third zone 853 may have a density of carbonaceous material between approximately 0.0 and 1.5 g/cc.
  • the first zone 851 may include pores having a width between approximately 0 and 40 nm
  • the second zone 852 may include pores having a width between approximately 0 and 35 nm
  • the third zone 853 may include pores having a width between approximately 0 and 30 nm.
  • the second zone 852 may not be defined for the tri-zone particle 850.
  • the first zone 851 may have a principal dimension Di between approximately 0 nm and 100 nm
  • the second zone 852 may have a principal dimension D2 between approximately 20 nm and 150 nm
  • the third zone 853 may have a principal dimension D3 of approximately 200 nm.
  • the unique layout of the tri-zone particle 850 and the relative dimensions, porosities, and electrical conductivities of the first zone 851, the second zone 852, and the third zone 853 can be selected and/or modified achieve a desired balance between minimizing the poly sulfide shuttle effect and maximizing the specific capacity of a host battery.
  • the pores may decrease in size and volume from one zone to other.
  • the tri-zone particle may consist entirely of one zone with a range of pore sizes and pores distributions (e.g., pore density).
  • the pores 861 associated with the first zone 851 or the first porosity region have relatively large widths and may be defined as macropores
  • the pores 862 associated with the second zone 852 or the second porosity region have intermediate- sized widths and may be defined as mesopores
  • the pores 863 associated with the third zone 853 or the third porosity region have relatively small widths and may be defined as micropores.
  • a group of tri-zone particles 850 may be joined together to form an aggregate (not shown for simplicity), and a group of the aggregates may be joined together to form an agglomerate (not shown for simplicity).
  • a plurality of mesopores may be interspersed throughout the aggregates formed by respective groups of the carbonaceous particles 800.
  • the first porosity region 811 may be at least partially encapsulated by the second porosity region 812 such that a respective aggregate may include one or more mesopores and one or more macropores.
  • each mesopore may have a principal dimension between 3.3 nanometers (nm) and 19.3 nm, and each macropore may have a principal dimension between 0.1 pm and 1,000 pm.
  • the tri-zone particle 850 may include carbon fragments intertwined with each other and separated from one another by at least some of the mesopores.
  • the tri-zone particle 850 may include a surfactant or a polymer that includes one or more of styrene butadiene rubber, polyvinylidene fluoride, poly acrylic acid, carboxyl methyl cellulose, polyvinylpyrrolidone, and/or polyvinyl acetate that can act as a binder to join a group of the carbonaceous materials together.
  • the tri-zone particle 850 may include a gel-phase electrolyte or a solid- phase electrolyte disposed within at least some of the pores.
  • the tri-zone particle 850 may have a surface area of exposed carbonaceous surfaces in an approximate range between 10 m 2 /g to 3,000 m 2 /g and/or a composite surface area (including sulfur micro-confined within pores) in an approximate range between 10 m 2 /g to 3,000 m 2 /g.
  • a composition of matter including a multitude of tri-zone particles 850 may have an electrical conductivity in an approximate range between 100 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi) and a sulfur to carbon weight ratio between approximately 1:5 to 10:1.
  • Figure 8C shows an example step function 800C representative of the average pore volumes in each of the regions of the tri-zone particle 850 of Figure 8B, according to some implementations. As discussed, the pores distributed throughout the tri-zone particle
  • the average pore volume may decrease based on a distance between a center of the tri-zone particle 850 and an adjacent zonae, for example, such that pores associated with the first zone
  • the interior region has a higher pore volume than the regions near the periphery.
  • the region with higher pore volume provides for high sulfur loading whereas the lower pore volume outer regions mitigate the migration of polysulfides during cell cycling.
  • the average pore volume in the inner region is approximately 3 cc/g
  • the average pore volume in the outermost region is -0.5 cc/g
  • the average pore volume in the intermediate region is between 0.5 cc/g and 3 cc/g.
  • FIG. 8D shows a graph 800D depicting an example distribution of pore volume versus pore width of carbonaceous particles described herein.
  • pores associated with a relatively high pore volume may have a relatively low pore width, for example, such that the pore width generally increases as the pore volume decreases.
  • pores having a pore width less than approximately 1.0 nm may be referred to as micropores
  • pores having a pore width between approximately 3 and 11 nm may be referred to as mesopores
  • pores having a pore width greater than approximately 24 nm may be referred to as macropores.
  • FIG. 9A shows a micrograph 900 of a plurality of carbonaceous structures 902, according to some implementations.
  • each of the carbonaceous structures 902 may have a substantially hollow a core region surrounded by various monolithic carbon growths and/or layering.
  • the monolithic carbon growths and/or layering may be examples of the monolithic carbon growths and/or layering described with reference to Figures 8A and 8B.
  • the carbonaceous structures 902 may include several concentric multi-layered fullerenes and/or similarly shaped carbonaceous structures organized at varying levels of density and/or concentration.
  • each of the carbonaceous structures 902 may depend on various manufacturing processes.
  • the carbonaceous structures 902 may, in some aspects, demonstrate poor water solubility.
  • non- covalent functionalization may be utilized to alter one or more dispersibility properties of the carbonaceous structures 902 without affecting the intrinsic properties of the underlying carbon nanomaterial.
  • the underlying carbon nanomaterial may be formative a sp 2 carbon nanomaterial.
  • each of the carbonaceous structures 902 may have a diameter between approximately20 and 500 nm.
  • groups of the carbonaceous structures 902 may coalesce and/or join together to form the aggregates 904.
  • groups of the aggregates 904 may coalesce and/or join together to form the agglomerates 906.
  • one or more of the carbonaceous structures 902, the aggregates 904, and/or the agglomerates 906 may be used to form the anode and/or the cathode of the battery 100 of Figure 1, the battery 200 of Figure 2, or the electrode 300 of Figure 3.
  • Figure 9B shows a micrograph 950 of an aggregate formed of carbonaceous material, according to some implementations.
  • the aggregate 960 may be an example of one of the aggregates 904 of Figure 9A.
  • exterior carbonaceous shell-type structures 952 may fuse together with carbons provided by other carbonaceous shell-type structures 954 to form a carbonaceous structure 956.
  • a group of the carbonaceous structures 956 may coalesce and/or join with one another to form the aggregate 1010.
  • a core region 958 of each of the carbonaceous structures 956 may be tunable, for example, in that the core region 958 may include various defined concentration levels of interconnected graphene structures, as described with reference to Figure 8 A and/or Figure 8B.
  • some of the carbonaceous structures 956 may have a first concentration of interconnected carbons approximately between 0.1 g/cc and 2.3 g/cc at or near the exterior carbonaceous shell-type structure 952.
  • Each of the carbonaceous structures 956 may have pores to transport lithium ions extending inwardly from toward the core region 1008.
  • the pores in each of the carbonaceous structures 956 may have a width or dimension between approximately 0.0 nm and 0.5 nm, between approximately 0.0 and 0.1 nm, between approximately 0.0 and 6.0 nm, or between approximately 0.0 and 35 nm.
  • Each carbonaceous structures 956 may also have a second concentration at or near the core region 958 that is different than the first concentration.
  • the second concentration may include several relatively lower-density carbonaceous regions arranged concentrically.
  • the second concentration may be lower than the first concentration at between approximately 0.0 g/cc and 1.0 g/cc or between approximately 1.0 g/cc and 1.5 g/cc.
  • the relationship between the first concentration and the second concentration may be used to achieve a balance between confining sulfur or poly sulfides within a respective electrode and maximizing the transport of lithium ions.
  • sulfur and/or polysulfides may travel through the first concentration and be at least temporarily confined within and/or interspersed throughout the second concentration during operational cycling of a lithium- sulfur battery.
  • the carbonaceous structures 956 may include CNO oxides organized as a monolithic and/or interconnected growths and be produced in a thermal reactor.
  • the carbonaceous structures 956 may be decorated with cobalt nanoparticles according to the following example recipe: cobalt(II) acetate (C4H6C0O4), the cobalt salt of acetic acid (often found as tetrahydrate Co(CH3CC>2)2 ⁇
  • suitable gas mixtures used to produce Carbon #29 and/or the cobalt decorated CNOs may include the following steps:
  • Carbonaceous materials described with reference to Figures 9A and 9B may include or otherwise be formed from one or more instances of graphene, which may include a single layer of carbon atoms with each atom bound to three neighbors in a honeycomb structure.
  • the single layer may be a discrete material restricted in one dimension, such as within or at a surface of a condensed phase.
  • graphene may grow outwardly only in the x and y planes (and not in the z plane).
  • graphene may be a two- dimensional (2D) material, including one or several layers with the atoms in each layer strongly bonded (such as by a plurality of carbon-carbon bonds) to neighboring atoms in the same layer.
  • graphene nanoplatelets may include multiple instances of graphene, such as a first graphene layer, a second graphene layer, and a third graphene layer, all stacked on top of each other in a vertical direction.
  • Each of the graphene nanoplatelets which may be referred to as a GNP, may have a thickness between 1 nm and 3 nm, and may have lateral dimensions ranging from approximately 100 nm to 100 pm.
  • graphene nanoplatelets may be produced by multiple plasma spray torches arranged sequentially by roll-to-roll (R2R) production.
  • R2R production may include deposition upon a continuous substrate that is processed as a rolled sheet, including transfer of 2D material(s) to a separate substrate.
  • the R2R production may be used to form the first thin film 310 and/or the second thin film 320 of the electrode 300 of Figure 3, for example, such that the concentration level of the first aggregates 312 within the first thin film 310 is different than the concentration level of the second aggregates 322 within the second thin film 320. That is, the plasma spray torches used in the R2R processes may spray carbonaceous materials at different concentration levels to create the first thin film 310 and/or the second thin film 320 using specific concentration levels of graphene nanoplatelets. Therefore, R2R processes may provide a fine level of tunability for the battery 100 of Figure 1 and/or the battery 200 or Figure 2.
  • Figures 10A and 10B show transmission electron microscope (TEM) images 1000 and 1050, respectively, of carbonaceous particles treated with carbon dioxide (CO2), according to some implementations.
  • the carbonaceous particles shown in Figures 10A and 10B may include or otherwise be formed from one or more instances of graphene, which may include a single layer of carbon atoms with each atom bound to three neighbors in a honeycomb structure.
  • Figure 11 shows a diagram 1100 depicting carbon porosity types of various carbonaceous aggregates, according to some implementations.
  • the carbonaceous aggregates described with reference to Figure 11 may be examples of the aggregates 904 of Figure 9A and/or the carbonaceous structures 956 of Figure 9B.
  • the carbonaceous aggregates described with reference to Figure 11 may be used to form the electrode 300 of Figure 3.
  • the aggregates may be formed from or may include a group of carbonaceous structures such as the carbonaceous structure 902 of Figure 9A or the carbonaceous structures 956 of Figure 9B.
  • the carbonaceous structures may be CNOs.
  • the carbonaceous structures may be used to form an electrode (such as the electrode 300 of Figure 3) having any of the porosity types shown in the diagram 1100.
  • the electrode may include any of a porosity type 1 1110, a porosity type II 1120, and a porosity type III 1130.
  • the porosity type 1 1110 may include a first pore 1111, a second pore 1112, and a third pore 1113, all sized with a principal dimension of less than 5 nm to retain polysulfides within the electrode. Some polysulfides may grow in size upon forming larger complexes and become immovably lodged within pores of the porosity type I 1110.
  • aggregates may be joined together to create pores of the porosity type II 1120 and/or porosity type III 1130 that can retain larger poly sulfides and/or polysulfide complexes.
  • Figure 12 shows a graph 1200 depicting pore size versus pore distribution of an example electrode, according to some implementations.
  • Carbon 1 refers to structured carbonaceous materials including mostly micropores (such as less than 5 nm in principal dimension)
  • Carbon 2 refers to structured carbonaceous materials including mostly mesopores (such as between approximately 20 nm to 50 nm in principal dimension).
  • an electrode suitable for use in one of the batteries disclosed herein may be prepared to have the pore size versus pore distribution depicted in the graph 1200.
  • Figure 13 shows a first graph 1300 and a second graph 1310 depicting battery performance per cycle number, according to some implementations.
  • the first graph 1300 shows the specific discharge capacity of an example battery employing an electrolyte 1302 disclosed herein relative to the specific discharge capacity of a conventional battery employing a conventional electrolyte.
  • the second graph shows the capacity retention of the battery employing the electrolyte 1302 relative to the capacity retention of the battery employing the conventional electrolyte.
  • the electrolyte 1302 may be one example of the electrolyte 130 of Figure 1 or the electrolyte 230 of Figure 2.
  • FIG 14 shows a bar chart 1400 depicting battery performance per cycle number, according to some implementations.
  • the bar chart 1400 depicts the specific discharge capacity per cycle number of an example battery employing an electrolyte 1402 disclosed herein relative to the specific discharge capacity per cycle number of a conventional battery employing a conventional electrolyte.
  • the electrolyte 1402 may be one example of the electrolyte 130 of Figure 1 or the electrolyte 230 of Figure 2.
  • the bar chart 1400 shows that employing the electrolyte 1402 in an example battery (such as the battery 100 of Figure 1 or the battery 200 of Figure 2) may increase the specific discharge capacity of the battery by approximately 28% at the 3 rd cycle number, by approximately 30% at the 50 th cycle number, and by approximately 39% at the 60 th as compared to a battery employing the conventional electrolyte.
  • Figure 15 shows a first graph 1500 and a second graph 1510 depicting battery performance per cycle number, according to some implementations.
  • the first graph 1500 shows the electrode discharge capacity per cycle number of an example lithium- sulfur coin cell employing an electrolyte 1502 disclosed herein relative to the electrode discharge capacity per cycle number of an example lithium-sulfur coin cell battery employing a conventional electrolyte
  • the second graph 1510 shows the capacity retention per cycle number of the lithium- sulfur coin cell battery employing the electrolyte 1502 relative to the electrode discharge capacity per cycle number of the lithium-sulfur coin cell battery employing the conventional electrolyte.
  • the electrolyte 1502 may be one example of the electrolyte 130 of Figure 1 or the electrolyte 230 of Figure 2.
  • the lithium- sulfur coin cell battery is cycled at a discharge rate of 1C (such as fully discharged within one hour), at 100% depth-of-discharge (DOD) and is kept at approximately at room temperature (68°F or 20°C).
  • Figure 16 shows a graph 1600 depicting electrode discharge capacity per cycle number, according to some implementations. Specifically, the graph 1600 depicts the electrode discharge capacity per cycle number of an example battery employing an electrolyte 1602 disclosed herein relative to the electrode discharge capacity of a conventional battery employing a conventional electrolyte.
  • the electrolyte 1602 may be one example of the electrolyte 130 of Figure 1 or the electrolyte 230 of Figure 2.
  • FIG. 17 shows another graph 1700 depicting electrode discharge capacity per cycle number, according to some implementations. Specifically, the graph 1700 depicts the electrode discharge capacity per cycle number of an example battery employing an electrolyte 1702 and solvent package 1704 disclosed herein relative to the electrode discharge capacity of a conventional battery employing a conventional electrolyte and solvent package.
  • FIG. 18 shows a graph 1800 depicting specific discharge capacity per cycle number for various TBT-containing electrolyte mixtures, according to some implementations.
  • “181” indicates an electrolyte without any TBT additions, resulting in a 0 M TBT concentration level
  • “181-25TBT” indicates an electrolyte prepared at a 25 M TBT concentration level and so on and so forth.
  • a 5M TBT concentration level may result in an approximate 70 mAh/g discharge capacity increase relative to the electrolyte without any TBT additions.
  • Figure 19 shows a first graph 1900 depicting electrode discharge capacity per cycle number and a second graph 1910 depicting electrode capacity retention per cycle number, according to some implementations.
  • the first graph 1900 depicts the electrode discharge capacity per cycle number of an example battery that includes a protective lattice disclosed herein relative to the electrode discharge capacity of an example battery that does not include the protective lattice disclosed herein.
  • the second graph 1910 depicts the electrode capacity retention per cycle number of an example battery that includes the protective lattice disclosed herein relative to the electrode capacity retention of an example battery that does not include the protective lattice disclosed herein.
  • the protective lattice may be one example of the protective lattice 402 of Figure 4.
  • Figure 20 shows a first graph 2000 depicting electrode discharge capacity per cycle number and a second graph 2010 depicting electrode capacity retention per cycle number, according to other implementations.
  • the first graph 2000 depicts the electrode discharge capacity per cycle number of an example battery that includes the polymeric network of Figure 7.
  • the second graph 2010 depicts the discharge capacity retention per cycle number of an example battery that includes the polymeric network of Figure 7.
  • the battery may be one example of the battery 100 of Figure 1 or the battery 200 of Figure 2.
  • Figure 21 shows a first graph 2100 depicting electrode discharge capacity per cycle number and a second graph 2110 depicting electrode capacity retention per cycle number, according to some other implementations.
  • the first graph 2100 depicts the electrode discharge capacity per cycle number of an example battery that includes the protective layer 516 of Figure 5.
  • the second graph 2110 depicts the discharge capacity retention per cycle number of an example battery that includes the protective layer 516 of Figure 5.
  • the battery may be one example of the battery 100 of Figure 1 or the battery 200 of Figure 2.
  • FIG 22 shows an example cathode 2200 having a body 2201 and a width 2205, according to some implementations.
  • the cathode 2200 may be one example of the electrode 300 of Figure 3.
  • the cathode 2200 may be similar to the electrode 300 of Figure 3 in many respects, such that description of like elements is not repeated herein.
  • the cathode 2200 includes a first porous carbonaceous region 2210 and a second porous carbonaceous region 2220 positioned adjacent to the first porous carbonaceous region 2210.
  • the first porous carbonaceous region 2210 may be formed of a first concentration level of carbonaceous materials, and the second porous carbonaceous region 2220 formed of a second concentration level of carbonaceous materials dissimilar to the first concentration level of carbonaceous materials.
  • the second porous carbonaceous region 2220 may have a lower concentration level of carbonaceous materials than the first porous carbonaceous region 2210 as shown in Figure 22.
  • additional porous carbonaceous regions maybe coupled with at least the second porous carbonaceous region.
  • these additional porous carbonaceous regions may be arranged in order of incrementally decreasing concentration levels of carbonaceous materials in a direction away from the first porous carbonaceous region 2210 to provide for complete ionic transport and electrical current tunability. That is, in one implementation, the second porous carbonaceous region 2220 may face a bulk electrolyte (e.g., provided in the liquid phase) and the first porous carbonaceous region 2210 of the cathode 2200 may be coupled with a current collector (not shown in Figure 22 for simplicity).
  • a bulk electrolyte e.g., provided in the liquid phase
  • denser carbonaceous regions such as the first porous carbonaceous region 2210, may facilitate higher levels of electrical conduction (shown in Figure 22 as “e ”) between adjacent contact points of carbonaceous materials, while sparser carbonaceous regions, such as the second porous carbonaceous region 2220, may facilitate higher levels of lithium ion transport associated with improved lithium-sulfur battery discharge-charge cycling relative to conventional lithium ion batteries.
  • additional carbonaceous regions coupled with and positioned adjacent to the second porous carbonaceous region 2220 may have a lower density of carbonaceous materials than the second porous carbonaceous region 2220. In this way, the additional carbonaceous regions of lower density may accommodate higher levels of lithium ion transport to, for example, permit for tuning of various performance characteristics of the electrode 300.
  • the first porous carbonaceous region 2210 may include first non-tri-zone particles 2211.
  • the configuration of the first non-tri-zone particles 2211 within the first porous carbonaceous region is one example configuration. Other placements, orientations, alignments and/or the like are possible for the non-tri-zone particles.
  • each non-tri-zone particle may be an example of one or more carbonaceous materials disclosed elsewhere in the present disclosure.
  • the first porous carbonaceous region 2210 may also include first tri-zone particles 2212 interspersed throughout the first non-tri-zone particles 2211 as shown in Figure 22, or positioned in any other placement, orientation, or configuration. Each first tri-zone particle 2212 may be one example of the tri-zone particle 850 of Figure 8B.
  • each of the first tri-zone-particles 2212 may include first carbon fragments 2213 intertwined with each other and separated from one another by mesopores 2214.
  • Each tri-zone-particle may have a first deformable perimeter 2215 configured to coalesce with adjacent first non-tri-zone particles 2211 and/or first tri zone particles 2212.
  • the first porous carbonaceous region 2210 may also include first aggregates 2216, where each aggregate includes a multitude of the first tri-zone particles 2212 joined together.
  • each first aggregate may have a principal dimension in a range between 10 nanometers (nm) and 10 micrometers (pm).
  • the mesopores 2214 may be interspersed throughout the first plurality of aggregates, where each mesopore has a principal dimension between 3.3 nanometers (nm) and 19.3 nm.
  • the first porous carbonaceous region 2210 may include first agglomerates 2217, where each agglomerate includes a multitude of the first aggregates 2216 joined to each other.
  • each first agglomerate 2217 may have a principal dimension in an approximate range between 0.1 pm and 1,000 pm.
  • Macropores 2218 may be interspersed throughout the first aggregates 2216, where each macropore may have a principal dimension between 0.1 pm and 1,000 pm.
  • one or more of the above-discussed carbonaceous materials, allotropes and/or structures may be one or more examples of that shown in Figures 9A and 9B.
  • the second porous carbonaceous may include second non-tri-zone particles 2221, which may be one example of the first non-tri-zone particles 2211.
  • the second porous carbonaceous region 2220 may include second tri-zone particles 2222, which may each be one example of each of the first tri-zone particles 2212 and/or may be one example of the tri zone particle 850 of Figure 8B.
  • each second tri-zone particle 2222 may include second carbon fragments 2223 intertwined with each other and separated from one another by the mesopores 2214.
  • Each second tri-zone particle 2222 may have a second deformable perimeter 2225 configured to coalesce with one or more adjacent second non-tri-zone particles 2221 or second tri-zone particles 2222.
  • the second porous carbonaceous region 2220 may include second aggregates 2226, where each second aggregate 2226 may include a multitude of the second tri-zone particles 2222 joined together.
  • each second aggregate 2226 may have a principal dimension in a range between 10 nanometers (nm) and 10 micrometers (pm).
  • the mesopores 2214 may be interspersed throughout the second aggregates 2226, each mesopore may have a principal dimension between 3.3 nanometers (nm) and 19.3 nm.
  • the second porous carbonaceous region 2220 may include second agglomerates 2227, each second agglomerate 2227 may include a multitude of the second aggregates 2226 joined to each other, where each agglomerate may have a principal dimension in an approximate range between 0.1 pm and 1,000 pm.
  • the macropores 2218 may be interspersed throughout the second plurality of aggregates, where each macropore having a principal dimension between 0.1 pm and 1,000 pm.
  • one or more of the above-discussed carbonaceous materials, allotropes and/or structures may be one or more examples of that shown in Figures 9A and 9B .
  • the first porous carbonaceous region 2210 and/or the second porous carbonaceous region 2220 may include a selectively permeable shell (not shown in Figure 22 for simplicity), which may form a separated liquid phase on the first porous carbonaceous region 2210 or the second porous carbonaceous region 2220, respectively.
  • An electrolyte such as any of the electrolytes disclosed in the present disclosure, may be dispersed within the first porous carbonaceous region and/or the second porous carbonaceous region for lithium ion transport associated with lithium-sulfur battery discharge-charge operational cycling.
  • the first porous carbonaceous region 2210 may have an electrical conductivity in an approximate range between 500 S/m to 20,000 S/m at a pressure of 12,000 pounds per square in (psi).
  • the second porous carbonaceous region 2220 may have an electrical conductivity in an approximate range between 0 S/m to 500 S/m at a pressure of 12,000 pounds per square in (psi).
  • the first agglomerates 2217 and/or second agglomerates 2227 may include aggregates connected to each other with one or more polymer-based binders.
  • the first tri-zone particles 2212 or the second tri-zone particles 2222 may each include a first porosity region (not shown in Figure 22 for simplicity) located around a center of a respective first tri-zone particle 2212 or second tri-zone particle 2222.
  • the first porosity region may include first pores.
  • a second porosity region (not shown in Figure 22 for simplicity) may surround the first porosity region.
  • the second porosity region may include second pores.
  • the first pores may define a first pore density
  • the second pores may define a second pore density that is different the first pore density.
  • the mesopores 2214 may be grouped into first mesopores and second mesopores (both not shown in Figure 22 for simplicity).
  • the first mesopores may have a first mesopore density
  • the second mesopores may have a second mesopore density that is different than the first mesopore density.
  • the macropores 2218 may be grouped into first macropores that may have a first pore density, and second macropores (both not shown in Figure 22 for simplicity) that may have a second pore density different than the first pore density.
  • the first porous carbonaceous region 2210 and/or the second porous carbonaceous region 2220 may nucleate sulfur, such as that necessary to facilitate operational discharge-charge cycling of any of the lithium-sulfur batteries disclosed by the present disclosure.
  • the cathode 2200 may have a sulfur to carbon weight ratio between approximately 1:5 to 10:1.
  • one or more electrically conductive additives may be dispersed within the first porous carbonaceous region 2210 and/or the second porous carbonaceous region 2220 to, for example, correspondingly influence discharge-charge cycling performance of the cathode 2200.
  • a protective sheath such as the protective lattice 402 of Figure 4, may be disposed on the cathode.
  • a phrase referring to “at least one of’ or “one or more of’ a list of items refers to any combination of those items, including single members.
  • “at least one of: a, b, or c” is intended to cover the possibilities of: a only, b only, c only, a combination of a and b, a combination of a and c, a combination of b and c, and a combination of a and b and c.

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EP22822712.0A 2021-07-23 2022-07-21 Lithium-schwefel-batteriekathode aus mehreren kohlenstoffhaltigen regionen Pending EP4374433A2 (de)

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US17/383,744 US11342561B2 (en) 2019-10-25 2021-07-23 Protective polymeric lattices for lithium anodes in lithium-sulfur batteries
US17/383,756 US12126024B2 (en) 2019-10-25 2021-07-23 Battery including multiple protective layers
US17/383,735 US11489161B2 (en) 2019-10-25 2021-07-23 Powdered materials including carbonaceous structures for lithium-sulfur battery cathodes
US17/383,803 US11309545B2 (en) 2019-10-25 2021-07-23 Carbonaceous materials for lithium-sulfur batteries
US17/383,793 US11398622B2 (en) 2019-10-25 2021-07-23 Protective layer including tin fluoride disposed on a lithium anode in a lithium-sulfur battery
US17/383,769 US20210359308A1 (en) 2019-10-25 2021-07-23 Carbon-scaffolded lithium-sulfur battery cathodes featuring a polymeric protective layer
US17/563,183 US11404692B1 (en) 2021-07-23 2021-12-28 Lithium-sulfur battery cathode formed from multiple carbonaceous regions
PCT/US2022/037905 WO2023004060A2 (en) 2021-07-23 2022-07-21 Lithium-sulfur battery cathode formed from multiple carbonaceous regions

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JP2024529937A (ja) 2024-08-14
WO2023004060A2 (en) 2023-01-26
KR20240036086A (ko) 2024-03-19
TW202308206A (zh) 2023-02-16

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