WO2024091355A1 - Structure d'électrode à gradient à double couche pour une puissance et une densité d'énergie optimisées dans des batteries - Google Patents

Structure d'électrode à gradient à double couche pour une puissance et une densité d'énergie optimisées dans des batteries Download PDF

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Publication number
WO2024091355A1
WO2024091355A1 PCT/US2023/033294 US2023033294W WO2024091355A1 WO 2024091355 A1 WO2024091355 A1 WO 2024091355A1 US 2023033294 W US2023033294 W US 2023033294W WO 2024091355 A1 WO2024091355 A1 WO 2024091355A1
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Prior art keywords
layer
electrode
porous structure
porosity
concentration
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PCT/US2023/033294
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English (en)
Inventor
Kevin Rhodes
Arjun Mendiratta
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Lyten, Inc.
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Publication date
Priority claimed from US17/972,472 external-priority patent/US20240234696A9/en
Priority claimed from US17/972,482 external-priority patent/US11870063B1/en
Application filed by Lyten, Inc. filed Critical Lyten, Inc.
Publication of WO2024091355A1 publication Critical patent/WO2024091355A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of 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
    • H01M4/58—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to batteries, and more particularly to optimizing power and energy density in batteries.
  • a dual-layer gradient electrode structure for optimizing power and energy density in batteries.
  • the electrode includes a first layer above an electrically conductive substrate, the first layer including a first plurality of carbon aggregates having a first porosity.
  • a second layer is above, at least in part, the first layer, the second layer having a second porosity, and including a second plurality of carbon aggregates.
  • the second plurality of carbon aggregates includes a first group of aggregates and a second group of aggregates.
  • the first group of aggregates is characterized by a first porous structure
  • the second group of aggregates is characterized by a second porous structure.
  • the second porous structure is characterized by a density greater than the first porous structure, and the second porosity is greater than the first porosity.
  • the first group of aggregates may be characterized by a first conductivity
  • the second group of aggregates may be characterized by a second conductivity
  • the second conductivity may be greater than the first conductivity
  • the first layer may have a concentration of carbon aggregates that may be different from a concentration of carbon aggregates in the second layer. Additionally, the first layer may have a concentration of carbon aggregates that is greater than a concentration of carbon aggregates in the second layer. Further, the first layer may have a thickness between 10 microns and 200 microns.
  • the second layer may entirely cover at least one surface of the first layer.
  • the second layer may be constructed as a series of rows, where each row of the series of rows may cover a portion of the first layer.
  • the second layer may be deposited as a series of rows onto the first layer, each row of the series of rows allowing for ion penetration across each surface of the row.
  • a third layer may be above, at least in part, the second layer, the third layer including a third plurality of carbon aggregates having a third porosity. Additionally, the third porosity may be less than the second porosity.
  • the first porous structure may include a first plurality of interconnected channels
  • the second porous structure may include a second plurality of interconnected channels
  • the first plurality of interconnected channels and the second plurality of interconnected channels may be coupled to one another.
  • the first plurality of interconnected channels may be coupled to the second plurality of interconnected channels.
  • the first plurality of interconnected channels may come in contact with (and/or interface at a surface layer) the second plurality of interconnected channels.
  • the first porous structure and/or the second porous structure may each include a first portion configured to provide a lithium ion conduit, a second portion configured to facilitate rapid lithium ion transport, and a third portion configured to confine lithium sulfide.
  • the electrode may be an anode or a cathode.
  • the first layer may be characterized by a first property to maximize ion density
  • the second layer may be characterized by a second property to maximize percolation channels.
  • the second porosity may be characterized by a continuous gradient from the first porous structure to the second porous structure.
  • the first porous structure may comprise a first set of agglomerates, the first set of agglomerates including interstitial spacing of a first dimension.
  • the second porous structure may comprise a second set of agglomerates, the second set of agglomerates including interstitial spacing of a second dimension.
  • the second layer may be a hierarchal layering based on the first porous structure, the second porous structure, the second porosity, and interstitial spacing. Additionally, the interstitial spacing may be based, at least in part, on a solvent used to create one or both of the first porous structure and the second porous structure. Further, a third layer may be above, at least in part, the second layer, the third layer including a third plurality of carbon aggregates, wherein the third layer is a buffer layer that minimizes interface growth or dendrite growth.
  • an electrode of a lithium-based battery may comprise a first layer disposed above an electrically conductive substrate, the first layer including a first plurality of carbon aggregates having a first porosity. Additionally, the electrode may comprise a second layer disposed above the first layer, the second layer including a second plurality of carbon aggregates, the second layer including a second porosity which is greater than the first porosity, where a first group of particles of the second layer has a first concentration of interacting functional groups, and a second group of particles of the second layer has a second concentration of the interacting functional groups, the second concentration being greater than the first concentration.
  • the interacting functional groups may be characterized by one or more of: polar groups, catalysts, solid state electrolyte particles, and a carbonaceous growth(s).
  • the polar groups may be coupled together by polar covalent bonds, and the polar groups include one or more of nitrogen groups, oxygen groups, and hydroxyl groups.
  • the catalysts may exhibit polar activity, and the catalysts may include one or more of tungsten carbide, and magnesium oxide.
  • the solid state electrolyte particles may include lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12).
  • the first concentration and the second concentration may be based on a frequency of the interacting functional groups within each of the first group of particles and the second group of particles respectively. Additionally, the interacting functional groups may impede polysulfide movement while allowing for Li ion transport.
  • the electrode may be a cathode. Additionally, the first layer may have a thickness between 10 microns and 200 microns.
  • the first group of particles may be characterized by a first porous structure, and the second group of particles may be characterized by a second porous structure. Additionally, the first porous structure may be characterized by a first interstitial spacing, and the second porous structure may be characterized by a second interstitial spacing.
  • the first concentration may be a first percent weight of the interacting functional groups, and the second concentration may be a second percent weight of the interacting functional groups. Additionally, the second porosity may be characterized by a continuous gradient from the first group of particles to the second group of particles. A concentration gradient may exist between the first concentration and the second concentration.
  • the interacting functional groups may act as polymer cages for poly sulfides. The first concentration may have a first amount of interaction with poly sulfides, and the second concentration may have a second amount of interaction with the polysulfides. Still yet, the interacting functional groups may substantially block polysulfides.
  • Figure 1 illustrates a dual-layer anode and cathode within a battery structure, in accordance with one embodiment.
  • Figure 2 illustrates a dual-layer electrode structure, in accordance with one embodiment.
  • Figure 3 illustrates a concentration gradient of a plurality of carbon aggregates within the second cast layer of a dual-layer electrode structure, in accordance with one embodiment.
  • Figure 4 illustrates a tri-layer electrode structure, in accordance with one embodiment.
  • Figure 5 illustrates rows within a second cast layer of a dual-layer electrode structure, in accordance with one embodiment.
  • Figure 6 illustrates a method for creating a dual-layer electrode structure, in accordance with one embodiment.
  • Thick cathodes may result in high energy density but reduce power density.
  • Very dense layers may reduce porosity (which may thereby provide high energy density), and may be limited by a thickness (due to reduce ion percolation pathway).
  • High power electrodes may provide high degrees of ion (such as Li+) percolation pathways to maximize the rate of ion transfer.
  • X employs A or B is intended to mean any of the natural inclusive permutations. That is, if X employs A, X employs B, or X employs both A and B, then “X employs A or B” is satisfied under any of the foregoing instances.
  • at least one of A or B means at least one of A, or at least one of B, or at least one of both A and B. In other words, this phrase is disjunctive.
  • the articles “a” and “an” as used in this application and the appended claims should generally be construed to mean “one or more” unless specified otherwise or is clear from the context to be directed to a singular form.
  • agglomerates include any resulting compounds and/or particles formed.
  • agglomerates may be a result of one of a variety of forces bringing two or more other compounds and/or particles together.
  • the term gradient refers to an increase or decrease in a magnitude of concentration.
  • gradient may include a hierarchal arrangement based on a stacking of a pore structure, agglomerates, interstitial spacing, and porosity items within a layer.
  • FIG. 1 illustrates a dual-layer anode and cathode within a battery structure 100, in accordance with one embodiment.
  • the battery structure 100 may be implemented in the context of any one or more of the embodiments set forth in any subsequent figure(s) and/or description thereof.
  • the battery structure 100 may be implemented in the context of any desired environment. Further, the aforementioned definitions may equally apply to the description below.
  • the battery structure 100 is comprised of a cathode 102, an anode 106, and a separator 104 encased within a body 108 (i.e. battery body).
  • the cathode 102 is comprised of a cathode current collector 102A, a first cathode cast layer 102B, and a second cathode cast layer 102C.
  • the anode 106 is comprised of an anode current collector 106A, a first anode cast layer 106B, and a second anode cast layer 106C.
  • the battery structure 100 represents just one configuration, and that other alterations (i.e., fixed, replaceable, cylindrical, prismatic, pouch, a plurality of individual cells organized as a pack, designed to emphasize increased power output vs. increased longevity, etc.) are envisioned.
  • the battery structure 100 shows both implementation within the cathode 102 and the anode 106.
  • the cast layers presented may exist in either of, or both of, the cathode 102 and the anode 106. Additionally, modifications in the application of the cast layers may be made to each of the cathode 102 and the anode 106 as needed (e.g. based on electrode specific requirements).
  • the first cathode cast layer 102B and the second cathode cast layer 102C may be optimized to limit lithium polysulfide transfer of the cathode 102.
  • each electrode (the cathode 102 and the anode 106) of the battery structure 100 may be composed of two distinct cast layers (or potentially more than two) to make up a cast electrode for a battery.
  • the bottommost layer (in contact with the current collection) may be composed of a relatively dense layer, the first cast layer (such as the first anode cast layer 106B and/or the first cathode cast layer 102B).
  • the first cast layer (dense layer) may include active materials (in its primary particle state) along with appropriate binder and optional conductive additive.
  • the first cast layer (dense layer) may have a limited thickness (i.e. needs to be thin enough to allow ion transfer).
  • the second cast layer (such as the second cathode cast layer 102C and/or the second anode cast layer 106C) may be cast on top of the first cast layer.
  • the second cast layer may utilize an active material which may be processed into a secondary aggregate where the porosity has been tuned.
  • the second cast layer may include a relevant binder and optional conductive additive.
  • the second cast layer may be significantly thicker than the first layer due the increased interparticle porosity developed between the aggregate structures.
  • first cast layer may have greater power density but may be limited in its thickness.
  • second cast layer may have lower power density but may have a thicker layer (due to increase porosity). In this manner, this dual structure provides for a porosity structure in the electrode that optimizes both energy density and lithium percolation channels.
  • the particle used within the first cast layer and/or the second cast layer may include a sulfurized carbon primary particle. Additionally, the particle may be applied using a spray dried technique.
  • the first cast layer (such as the first cathode cast layer 102B and/or the first anode cast layer 106B) may above on an electrically conductive substrate, the first cast layer including a first plurality of carbon aggregates having a first porosity.
  • the first cast layer (or any of the cast layers) may be located above a foregoing layer, the cast layer having some direct contact (at least in part) with the foregoing layer.
  • the cast layer may have gaps and/or impurities which may prevent a complete deposition onto the foregoing surface.
  • the first cast layer may have a concentration of carbon aggregates that is different from a concentration of carbon aggregates in the second layer.
  • the first cast layer may have a concentration of carbon aggregates that is greater than a concentration of carbon aggregates in the second layer.
  • the first layer may have a thickness between 10 microns and 200 microns.
  • the first cast layer may be characterized by a first property to maximize ion density, and the second layer may be characterized by a second property to maximize percolation channels.
  • a second cast layer (such as the second cathode cast layer 102C and/or the second anode cast layer 106C) may be above, at least in part, the first layer.
  • the second cast layer may be constructed as a series of rows (described in further detail within the context of Figure 5), each row of the series of rows covering a portion of the first cast layer wherein each row of the series of rows allows for ion penetration across each surface of the row.
  • the second cast layer may be a hierarchal layering characterized by the first porous structure, the second porous structure, the second porosity, and interstitial spacing. Further, the interstitial spacing may be based, at least in part, on a solvent used to create one or both of the first porous structure and the second porous structure.
  • the second layer may cover the first layer entirely.
  • the second cast layer may have a second porosity, and include a second plurality of carbon aggregates.
  • the second plurality of carbon aggregates may include a first group of the second plurality of carbon aggregates, where the first group has a first porous structure.
  • the second plurality of carbon aggregates may include a second group of the second plurality of carbon aggregates.
  • the second group may have a second porous structure that is denser than the first porous structure, and the second porosity may be greater than the first porosity.
  • each of the first porous structure and the second porous structure may each include a plurality of interconnected channels, and each of the interconnected channels may include a first portion configured to provide a lithium ion conduit, a second portion configured to facilitate rapid lithium ion transport, and a third portion configured to confine lithium sulfide.
  • the second porosity may be characterized by a continuous gradient from the first porous structure to the second porous structure.
  • the first porous structure may comprise a first set of agglomerates, the first set of agglomerates including interstitial spacing of a first dimension
  • second porous structure comprise a second set of agglomerates, the second set of agglomerates including interstitial spacing of a second dimension.
  • a third layer may be above, at least in part, the second layer, the third layer including a third plurality of carbon aggregates having a third porosity, where the third porosity is less than the second porosity. Additionally, the third layer may include a third plurality of carbon aggregates, where the third layer is a buffer layer that minimizes interface growth or dendrite growth.
  • an electrode component of the battery comprises an anode 106 or a cathode 102.
  • the cathode 102 and anode 106 may be comprised of various forms of carbon-based materials including graphite and graphene.
  • the graphite and/or graphene construction materials may also include additives in the form of silicone, silicon-based alloys, and/or nano-structured lithium-titanate.
  • the cathode 102 and anode 106 may contain any of a variety of electrolyte compounds to facilitate lithium ion transfer through the separator 104.
  • Such materials may include, by way of non-limiting examples, simple concentrated saline, lithium cobalt oxide (LiCoCh), lithium iron phosphate (LiFePCE), lithium manganese oxide (LiMmCh), lithium nickel manganese cobalt oxide (LiNiMnCoCh), and/or Ga-doped lithium lanthanum zirconium oxide (LivLasZnOn).
  • a lithium battery electrolyte composition may be composed of solvent, lithium salt, and a variety of additives.
  • the lithium battery solvent may include cyclic carbonate (PC, EC), chain carbonate (DEC, DMC, EMC), and/or carboxylic acid esters (MF, MA, EA, MA, MP, etc.).
  • the lithium salt element of the electrolyte may comprise a variety of compounds including LiPFe, LiClC>4, LiBF4, LiAsFe, etc.
  • additives within the electrolyte may include film-forming additives, conductive additives, flame retardant additives, overcharge protection additives, additives that may control H2O and HF content in the electrolyte, additives that may improve low-temperature performance, and other functional additives.
  • an electrolyte compound may be employed in liquid, gelatinous, or solid form, or a combination thereof.
  • the separator 104 may comprise a very porous structure, in the pores of which liquid resides, thus creating a closed membrane-like structure through which lithium ions may freely pass and through which free electrons may not pass.
  • a lithium-ion separator may include pore size ranges from 30 to 100 nanometers.
  • a separator may feature a porosity of 30 to 50 percent, which may allow for retention of adequate liquid electrolyte to enable the pores to close in the event that a battery cell may possibly overheat.
  • modern lithium ion battery structures may include polyolefin as the separator 104.
  • Polyolefin may be produced a class of polymer produced from olefin by polymerizing olefin ethylene. It should be appreciated that, where ethylene may originate from a petrochemical source, polyolefin may be made from polyethylene, polypropylene, and/or a laminate comprised of a combination of both polyethylene and polypropylene.
  • historic and/or traditional early-generation separator materials may include rubber, glass fiber mat, cellulose, polyethylene plastic, porous polyolefin films, nylon or cellophane, and even wood.
  • the first cast layer may be very dense with very few percolation ion channels.
  • the percolation ion channels may allow (and thereby limit) penetration of ions (e.g. lithium).
  • the first cast layer may be less than a few micros thick (which may be directly contingent upon rate capability limitations), such as, in one embodiment, between 10 microns and 200 microns.
  • an electrode of a lithium-based battery may comprise a first layer disposed above an electrically conductive substrate, the first layer including a first plurality of carbon aggregates having a first porosity.
  • the electrode may comprise a second layer disposed above the first layer, the second layer including a second plurality of carbon aggregates, the second layer including a second porosity which is greater than the first porosity, where a first group of particles of the second layer has a first concentration of interacting functional groups, and a second group of particles of the second layer has a second concentration of the interacting functional groups, the second concentration being greater than the first concentration.
  • the interacting functional groups may be characterized by one or more of: polar groups, catalysts, solid state electrolyte particles, and a carbonaceous growth(s).
  • the polar groups may be coupled together by polar covalent bonds, and the polar groups include one or more of nitrogen groups, oxygen groups, and hydroxyl groups.
  • the catalysts may exhibit polar activity, and the catalysts may include one or more of tungsten carbide, and magnesium oxide.
  • the solid state electrolyte particles may include lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12).
  • the first concentration and the second concentration may be based on a frequency of the interacting functional groups within each of the first group of particles and the second group of particles respectively. Additionally, the interacting functional groups may impede polysulfide movement while allowing for Li ion transport. [0048] In one embodiment, within the context of using interacting functional groups, the electrode may be a cathode. Additionally, the first layer may have a thickness between 10 microns and 200 microns.
  • the first group of particles may be characterized by a first porous structure, and the second group of particles may be characterized by a second porous structure. Additionally, the first porous structure may be characterized by a first interstitial spacing, and the second porous structure may be characterized by a second interstitial spacing.
  • the first concentration may be a first percent weight of the interacting functional groups
  • the second concentration may be a second percent weight of the interacting functional groups.
  • the second porosity may be characterized by a continuous gradient from the first group of particles to the second group of particles. A concentration gradient may exist between the first concentration and the second concentration.
  • the interacting functional groups may act as polymer cages for poly sulfides. The first concentration may have a first amount of interaction with poly sulfides, and the second concentration may have a second amount of interaction with the polysulfides. Still yet, the interacting functional groups may substantially block polysulfides.
  • Figure 2 illustrates a dual-layer electrode structure 200, in accordance with one embodiment.
  • the dual-layer electrode structure 200 may be implemented in the context of any one or more of the embodiments set forth in any previous and/or subsequent figure(s) and/or description thereof.
  • the dual-layer electrode structure 200 may be implemented in the context of any desired environment. Further, the aforementioned definitions may equally apply to the description below.
  • the dual-layer electrode structure 200 may be comprised of a current collector 202, a first cast layer 204 (in contact with the current collector 202), and a second cast layer 206 applied over the first cast layer 204.
  • the second cast layer 206 may comprise multiple sublayers, including sublayer 206a, sublayer 206b, sublayer 206c, and sublayer 206d.
  • the sublayers 206a through 206d may each include group of carbon aggregates (which may or may not be different from an adjoining sublayer). Additionally, the sublayers 206a through 206d may be hierarchical according to a concentration gradient 208.
  • the first group of carbon aggregates may be characterized by a first conductivity
  • the second group of carbon aggregates may be characterized by a second conductivity.
  • the second conductivity may be greater than the first conductivity.
  • the first cast layer 204 may have a concentration of carbon aggregates that may be different from a concentration of carbon aggregates in the second cast layer 206. Additionally, the first cast layer 204 may have a concentration of carbon aggregates that may be greater than a concentration of carbon aggregates in the second cast layer 206. In addition, the first cast layer 204 may have a thickness between 10 microns and 200 microns. The first cast layer 204 may be characterized by a first property to maximize ion density, and the second cast layer 206 may be characterized by a second property to maximize percolation channels.
  • the second cast layer 206 may be a hierarchal layering based on the first porous structure, the second porous structure, the second porosity, and interstitial spacing. Further still, the interstitial spacing may be based, at least in part, on a solvent used to create one or both of the first porous structure and the second porous structure.
  • gradient lithium ion traversal may be achieved by way of chemical interaction, catalytic interaction, polar group interaction, etc.
  • charged materials may include tungsten sulfide and/or tungsten carbide.
  • the polar elements in these scenarios may include, but are not limited to, nitrogen or oxygen groups, hydroxyl groups, where catalytic elements may or may not include tungsten carbide and magnesium oxide.
  • the second cast layer 206 may cover the first cast layer 204 entirely.
  • an electrode structure may include a type of scaffolding framework designed to preserve the rough three- dimensional "shape" (e.g., to minimize fluctuation) of a group of sublayers.
  • one layer of such a scaffolding model may feature a first sublayer comprised nearly entirely of lithium electrolyte.
  • a next layer may include a base structure of carbon nanofibers (or a similar carbon aggregate) and/or graphite material designed to retain a sort of consistent form.
  • subsequent sublayers may be applied that feature slightly more carbon-based structure as the layers build upon one another and get nearest the battery separator component.
  • the sublayer group in question may incorporate almost pure lithium metal nearest the battery collector component with a layer of one or more alloyed lithium composites nearer the separator.
  • the scaffold-like structure may be employed in the form of an etching within the electrolyte where the scaffolding-type system is essentially anchored down within the electrode for stability.
  • the sublayers of thin lithium may be pre-formed with different concentrations of scaffolding-type material and effectively “rolled-out” into place.
  • different concentrations of lithium alloy sublayers may be put together before assembly into a group of sublayers in the electrolyte.
  • a pre-formed material may be fashioned using an aqueous n-methyl-2- pyrrolidone (NMP)-based slurry ready to be applied in sublayers according to specific design requirements.
  • NMP aqueous n-methyl-2- pyrrolidone
  • the dual-layer electrode structure 200 of the electrode may be an anode or a cathode.
  • Figure 3 illustrates a concentration gradient of a plurality of carbon aggregates within the second cast layer of a dual-layer electrode structure 300, in accordance with one embodiment.
  • the dual-layer electrode structure 300 may be implemented in the context of any one or more of the embodiments set forth in any previous and/or subsequent figure(s) and/or description thereof.
  • the dual-layer electrode structure 300 may be implemented in the context of any desired environment. Further, the aforementioned definitions may equally apply to the description below.
  • the dual-layer electrode structure 300 may be comprised of a current collector 302, a first cast layer 304 (in direct contact with the current collector 302), and a second cast layer 306 applied over the first cast layer 304.
  • the second cast layer 306 may comprise a group of carbon aggregates including a first carbon aggregate sublayer 306a having a first porous structure, a second carbon aggregate sublayer 306b having a second porous structure, a third carbon aggregate sublayer 306c having a third porous structure, and a fourth carbon aggregate sublayer 306d having a fourth porous structure.
  • the second cast layer 306 is visibly shown with varying levels of concentrations throughout each of the first carbon aggregate sublayer 306a, the second carbon aggregate sublayer 306b, the third carbon aggregate sublayer 306c, and/or the fourth carbon aggregate sublayer 306d. It is to be appreciated that the concentration can be predetermined and set (e.g. at the time of spray drying the particles). Each sublayer (306a through 306d) may each have specific porous structures based on preconfigured considerations. In this manner, the layering of the sublayers 306a through 306d may include a gradient of varying concentrations of particles.
  • some or all of the porous structures of the sublayers 306a through 306d may include a plurality of interconnected channels.
  • each of the interconnected channels may be configured for a particular effect.
  • a first layer may be configured to provide a lithium ion conduit
  • a second layer may be configured to facilitate rapid lithium ion transport
  • a third layer may be configured to confine lithium sulfide.
  • each sublayer may include groupings and/or portions where each groupings and/or portions may be configured specifically for Ei ion conduit, rapid Li ion transport, and/or to confine lithium sulfide.
  • polysulfides may be filtered in higher concentrations within each sublayer as the layers stack up closer to the separator.
  • each of the porous structures of the sublayers 306a through 306d may comprise a set of agglomerates and the agglomerates may include interstitial spacing of varying dimension (for each of the sublayers).
  • Each sublayer therefore may have specific and preconfigured conditions to perform predetermined agglomerates, and resulting interstitial spacing.
  • agglomerates may form through various mechanisms.
  • electrostatic forces between very small (nanoscale) particles may bring about the agglomeration of two or more disparate particles.
  • formation of solid bridges between particles may form upon evaporation following spraying of an additional liquid.
  • thermal effects may bring about agglomeration through, for example, sintering or glass transition. It is to be appreciated that the agglomerates may form as well based on the spray-drying technique, the solvent used in the application, etc.
  • FIG. 4 illustrates a tri-layer electrode structure 400, in accordance with one embodiment.
  • the tri-layer electrode structure 400 may be implemented in the context of any one or more of the embodiments set forth in any previous and/or subsequent figure(s) and/or description thereof.
  • the tri-layer electrode structure 400 may be implemented in the context of any desired environment. Further, the aforementioned definitions may equally apply to the description below.
  • the tri-layer electrode structure 400 may be comprised of a current collector 402, a first cast layer 404 (in direct contact with the current collector 402), a second cast layer 406 applied over the first cast layer 404, and a third cast layer 408 applied over the second cast layer 406.
  • the second cast layer 406 may be constructed and configured in a manner similar to the second cast layer 306.
  • the third cast layer 408 may include a third plurality of carbon aggregates having a third porosity. This third porosity may differ (and in some instances be less than) the porosity of the second cast layer 406 having a second porosity. Alternatively, the third porosity may be greater than the second porosity.
  • the second porosity may be characterized by a continuous gradient from the first porous structure to the second porous structure (consistent with the discussion of the second cast layer 306 and the concentration gradient 208). It should be appreciated that greater porosity may yield greater throughput and increased ability for lithium ions to pass (more-or-less unhindered) through a given sublayer of the second cast layer.
  • the third cast layer 408 may be configured to have gradient (or varying concentration) sublayers as well, consistent with that shown with respect to the second cast layer 306.
  • the third cast layer 408 may act as a buffer layer that minimizes interface growth or dendrite growth.
  • the third layer may be a polyvinylidene fluoride (PVDF) and/or a polyethylene oxide material used in the production of composite electrodes to form an essentially non-permeable (or solid) membrane designed to help prevent the electrolyte from reacting with the surface of the lithium in the electrode.
  • PVDF material may be designed without any inherent porosity so that it may allow free transfer of lithium ions and may thus act as a type of capacitor (e.g., with minimized impedance) for the electrode in question.
  • the PVDF material may be prepared as a solution of one to two percent PVDF mixed with a lithium storage material like silicon, tin, and/or graphite. Further still, a conductive additive like carbon fibers, alumina, and/or lanthanum zirconium oxide may also be added to the PVDF material solution. Further still, the PVDF material layer may be applied in a thickness of approximately 10 microns in depth. Alternatively, the PVDF material layer may be applied to fit design specifications requiring fewer than or greater than 10 microns.
  • Figure 5 illustrates rows within a second cast layer of a dual-layer electrode structure 500, in accordance with one embodiment.
  • the dual- layer electrode structure 500 may be implemented in the context of any one or more of the embodiments set forth in any previous and/or subsequent figure(s) and/or description thereof.
  • the dual-layer electrode structure 500 may be implemented in the context of any desired environment. Further, the aforementioned definitions may equally apply to the description below.
  • the dual-layer electrode structure 500 may be comprised of a current collector 502, a first cast layer 504 (in direct contact with the current collector 502), and a second cast layer 506 applied over the first cast layer 504.
  • the second cast layer 506 may be deposited as a series of rows 508 onto the first cast layer 504, with a channel 510 between each of the rows 508.
  • channels 510 between each of the rows 508 may allow for lithium ion penetration across each surface of the row of the second cast layer 506.
  • the channels 510 between each of the row 508 may be created by etching the second cast layer 506 to expose a subset of the first cast layer 504. It is to be appreciated that other techniques (other than etching) may be applied as appropriate to create the rows 508. Additionally, a laser may be employed to effectively etch channels into one or more sublayers of second cast layer 506.
  • the rows 508 may be configured to allow for differing shape, width, and/or depth, depending upon particular design specifications (which may provide for greater surface area contact and increased capacitance within the electrolyte).
  • the second cast layer 506 may include a concentration gradient (such as the concentration gradient 208) as disclosed herein.
  • the series of rows 508 may be substantially parallel (one row to the next), and may specifically designed as desired (diagonally aligned, perpendicular to a principal axis, etc.).
  • additional layers may be applied above the second cast layer 506, where each of those additional layers may (or may not) also etch out rows.
  • a third cast layer (such as the third cast layer 408) may be layered on top of the second cast layer 506 and may serve as an initial barrier.
  • the rows 508 of the second cast layer 506 may therefore be configured to maximize transport pathways and surface area for ion absorption. Further, including the channels 510 in various sublayers of the second cast layer 506 may bring about the result of providing diffusion pathways within the electrode layers to facilitate and maximize lithium ion traversal.
  • Figure 6 illustrates a method 600 for creating a dual-layer electrode structure, in accordance with one embodiment.
  • a first cast layer is created, using a first particle, applied using cast film. See operation 602.
  • the first layer may have a thickness between 10 microns and 200 microns.
  • the first particle may be configured prior to be applied.
  • a first sublayer, located on top of the first cast layer may be created at a first porosity by applying spray drying. See operation 604.
  • a second sublayer, located on top of the first sublayer may be created at a second porosity by applying spray drying. See operation 606.
  • a third sublayer, located on top of the second sublayer may be created at a third porosity by applying spray drying. See operation 608.
  • the first sublayer, the second sublayer, and/or the third sublayer may comprise a second cast layer, layered on top of the first cast layer.
  • spray drying may incorporate depositing particles to create a secondary pore structure. Additionally, the pores created within structure may form agglomerates comprising interstitial spaces between particles.
  • the secondary pore structure may be comprised of carbon nano-onion (CNO) to form a primary pore structure.
  • spray drying may incorporate the practice of employing different types of particles with different size channels. Further still, the difference size channels may be manifested as different channel densities and/or different porosity measures. By way of example, the process of spray drying particles may actually modify fundamental secondary particles so as to further promote a hierarchical sublayer structure.
  • the spray-dryer may be employed to create a gradient multi-sublayer structure comprised of different types of particles in the different sublayers.
  • multiple sublayers of different types of particles may be deposited through particle manipulation, sublayer-upon-sublayer, to construct different gradient porosity and/or density structures.
  • the same types of particles may also be used in different sublayers, in one or more different porosities and/or densities, to achieve a gradient concentration result.
  • different particles may be applied by spray drying in any combination to achieve desired porosity and/or density thresholds.
  • the particles applied in the gradient sublayers via spray drying may be comprised of, but may not be limited to, varying states of carbon particles, tungsten sulfide, tungsten oxide, magnesium oxide, lithium lanthanum, and/or zirconium oxide. Additionally, different percentage weights or concentrations of tungsten sulfide, tungsten oxide, magnesium oxide, lithium lanthanum, and/or zirconium oxide may be applied via spray drying. By way of just one non-exhaustive example, the tungsten sulfide and/or tungsten oxide may be applied in a model wherein a top sublayer may yield a 10% concentration while the bottom sublayer may yield a 1 % concentration.
  • concentrations cascading from lowest-to-highest may be just as desirable as concentrations cascading from highest- to-lowest, depending on the specific application for a specific electrode layer.
  • the highest-concentration sublayer may be most desirable in closest proximity to the battery separator (such as the separator 104) positioned between the anode and cathode.
  • the sublayer of the electrolyte compound may be employed in liquid, gelatinous, or solid form, or a combination thereof.
  • At least one component defined by the claims is implemented at least partially as an electronic hardware component, such as an instruction execution machine (e.g., a processor-based or processor-containing machine) and/or as specialized circuits or circuitry (e.g., discreet logic gates interconnected to perform a specialized function).
  • an instruction execution machine e.g., a processor-based or processor-containing machine
  • specialized circuits or circuitry e.g., discreet logic gates interconnected to perform a specialized function.
  • Other components may be implemented in software, hardware, or a combination of software and hardware. Moreover, some or all of these other components may be combined, some may be omitted altogether, and additional components may be added while still achieving the functionality described herein.
  • the subject matter described herein may be embodied in many different variations, and all such variations are contemplated to be within the scope of what is claimed.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

Une structure d'électrode à gradient à double couche est prévue pour optimiser la puissance et la densité d'énergie dans des batteries. Lors de l'utilisation, pour une électrode d'une batterie à base de lithium, l'électrode comprend une première couche au-dessus d'un substrat électroconducteur, la première couche comprenant une première pluralité d'agrégats de carbone ayant une première porosité. En outre, une seconde couche est au-dessus, au moins en partie, de la première couche, de la seconde couche ayant une seconde porosité, et comprenant une seconde pluralité d'agrégats de carbone. La seconde pluralité d'agrégats de carbone comprend un premier groupe d'agrégats et un second groupe d'agrégats. Le premier groupe d'agrégats est caractérisé par une première structure poreuse, et le second groupe d'agrégats est caractérisé par une seconde structure poreuse. En outre, la seconde structure poreuse est caractérisée par une densité supérieure à la première structure poreuse, et la seconde porosité est supérieure à la première porosité.
PCT/US2023/033294 2022-10-24 2023-09-20 Structure d'électrode à gradient à double couche pour une puissance et une densité d'énergie optimisées dans des batteries WO2024091355A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US17/972,472 2022-10-24
US17/972,472 US20240234696A9 (en) 2022-10-24 Dual layer gradient electrode structure for optimized power and energy density in batteries
US17/972,482 2022-10-24
US17/972,482 US11870063B1 (en) 2022-10-24 2022-10-24 Dual layer gradient cathode electrode structure for reducing sulfide transfer

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015048583A1 (fr) * 2013-09-27 2015-04-02 Sensel, Inc. Systèmes de détecteur à capteur tactile et procédé
US20160308218A1 (en) * 2015-04-14 2016-10-20 24M Technologies, Inc. Semi-solid electrodes with porous current collectors and methods of manufacture
US20210036312A1 (en) * 2019-07-30 2021-02-04 Lyten, Inc. 3d self-assembled multi-modal carbon-based particles integrated into a continuous electrode film layer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015048583A1 (fr) * 2013-09-27 2015-04-02 Sensel, Inc. Systèmes de détecteur à capteur tactile et procédé
US20160308218A1 (en) * 2015-04-14 2016-10-20 24M Technologies, Inc. Semi-solid electrodes with porous current collectors and methods of manufacture
US20210036312A1 (en) * 2019-07-30 2021-02-04 Lyten, Inc. 3d self-assembled multi-modal carbon-based particles integrated into a continuous electrode film layer

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