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WO2025075844A1 - Materials and methods for all-solid-state batteries - Google Patents

Materials and methods for all-solid-state batteries Download PDF

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Publication number
WO2025075844A1
WO2025075844A1 PCT/US2024/048330 US2024048330W WO2025075844A1 WO 2025075844 A1 WO2025075844 A1 WO 2025075844A1 US 2024048330 W US2024048330 W US 2024048330W WO 2025075844 A1 WO2025075844 A1 WO 2025075844A1
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WO
WIPO (PCT)
Prior art keywords
cathode
battery
binder
electrolyte
mpa
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
PCT/US2024/048330
Other languages
French (fr)
Inventor
Hailong Lyu
Sibo NIU
Jack Kivi
Nicholas S. GRUNDISH
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Energy Exploration Technologies Inc
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Energy Exploration Technologies Inc
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Filing date
Publication date
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Publication of WO2025075844A1 publication Critical patent/WO2025075844A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
    • H01M4/0447—Forming after manufacture of the electrode, e.g. first charge, cycling of complete cells or cells stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure is directed to a method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
  • a battery comprising: (a) a cathode electrode comprising: (i) a first substrate and (ai) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and (b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and (c) an anode electrode and wherein the battery is substantially solvent-free.
  • FIGURE 1 depicts the schematic diagram of the layer-by-layer solvent-free process for the all-solid-state lithium metal battery preparation.
  • ambient temperature and “room temperature” as used herein are understood in the art and refer generally to a temperature from about 20 °C to about 35 °C.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1 , 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.
  • spatially relative terms such as “beneath,” “below,” “lower,” “above,” “upper,” “bottom,” “top,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly.
  • the melting point of the first binder can be about 30 °C to about 70 °C, about 40 °C to about 70 °C, about 50 °C to about 70 °C, about 60 °C to about 70 °C, about 30 °C to about 150 °C, about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on.
  • the first binder can comprise polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
  • the first binder can be present in an amount greater than 0 wt% to about 20 wt%, as calculated based on a total weight of a cathode composite material. In certain exemplary and unlimiting aspects, the first binder can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more.
  • the first binder can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the first binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt% to about 10 wt%, or about 3.4 wt% to about 18.7 wt%, and so on.
  • the at least one electrolyte can be present in the cathode composite material in an amount greater than 0 wt% to about 50 wt%, as calculated based on a total weight of a cathode composite material.
  • the at least one electrolyte can be present in the cathode composite material in an amount of about 50 wt% or less, about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, about 5 wt% or less, about 1 wt% or less.
  • the at least one electrolyte can be present in the cathode composite material in an amount greater than 0 wt% to about 50 wt%, including exemplary values of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, and about 45 wt%.
  • the at least one electrolyte can be present in the cathode composite material in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the one or more fillers can be present in any amount that suits the desired application.
  • the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%, as calculated based on a total weight of a cathode composite material.
  • the one or more fillers can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more.
  • the one or more fillers can be present in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 2 wt% or less.
  • the one or more fillers can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%.
  • the cathode composite material can be hot pressed into the first substrate at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more.
  • the cathode composite material can be hot pressed into the first substrate at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less.
  • the cathode composite material can be hot pressed into the first substrate at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
  • the electrolyte material can further comprise a second binder having a melting point equal to or less than about 70 °C.
  • the second binder can comprise any polymeric material known in the art and suitable for the desired application with a melting point equal to or less than about 150 °C, equal to or less than about 140 °C, equal to or less than about 130 °C, equal to or less than about 120 °C, equal to or less than about 110 °C, equal to or less than about 100 °C, equal to or less than about 90 °C, equal to or less than about 80 °C, equal to or less than about 70 °C, equal to or less than about 60 °C, equal to or less than about 50 °C, equal to or less than about 40 °C, or equal to or less than about 30 °C.
  • the second binder can have a melting point of about 30 °C to about 150 °C, including exemplary values of about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, about 120 °C, about 130 °C, and about 140 °C. It is understood that the second binder can have a melting point that falls within any two of the disclosed above values of ranges.
  • the melting point of the second binder can be about 30 °C to about 70 °C, or about 40 °C to about 70 °C, or about 50 °C to about 70 °C, or about 60 °C to about 70 °C, or about 30 °C to about 150 °C, or about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on.
  • the electrolyte material can optionally comprise additional fillers and/or salts.
  • the electrolyte material can comprise additional ceramic materials, additional inorganic salts, and possible polymers that are elected from any of the disclosed herein lists.
  • the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less.
  • the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C.
  • the electrolyte layer is hot pressed with the cathode electrode at a temperature having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
  • the interfacial material can further comprise a third binder.
  • the third binder can be any of the disclosed above polymer materials having a melting point equal to or less than about 150 °C, equal to or less than about 140 °C, equal to or less than about 130 °C, equal to or less than about 120 °C, equal to or less than about 110 °C, equal to or less than about 100 °C, equal to or less than about 90 °C, equal to or less than about 80 °C, equal to or less than about 70 °C, equal to or less than about 60 °C, equal to or less than about 50 °C, equal to or less than about 40 °C, or equal to or less than about 30 °C.
  • the third binder can have a melting point equal to or greater than about 30 °C, equal to or greater than about 40 °C, equal to or greater than about 50 °C, equal to or greater than about 60 °C, equal to or greater than about 70 °C, equal to or greater than about 80 °C, equal to or greater than about 90 °C, equal to or greater than about 100 °C, equal to or greater than about 110 °C, equal to or greater than about 120 °C, equal to or greater than about 130 °C, equal to or greater than about 140 °C.
  • the melting point of the third binder can be about 30 °C to about 70 °C, or about 40 °C to about 70 °C, or about 50 °C to about 70 °C, or about 60 °C to about 70 °C, or about 30 °C to about 150 °C, or about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on.
  • the third binder is the same as the first binder. Yet, in other aspects, the third binder is different from the first binder. In some aspects, the third binder is the same as the second binder. Yet, in other aspects, the third binder is different from the second binder. In some aspects, the third binder is the same as the first binder and the second binder. Yet, in other aspects, the third binder is different from the first binder and the second binder.
  • the third binder can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%.
  • the third binder can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the third binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt % to about 10 wt%, or about 3.4 wt% to about 19 wt%, and so on.
  • the method disclosed herein comprises hot pressing the interfacial layer with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
  • the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 80 MPa, or about 30 MPa to about 55 MPa, or about 45 MPa to about 95 MPa and so on.
  • the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C to about 80 °C. Yet in still further aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more.
  • the anode electrode comprises Li metal, Li-alloys, carbon-based anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof.
  • the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery.
  • the anode electrode is formed in situ on a bare current collector, where the current collector can comprise any of the disclosed herein materials. In some aspects, such a battery can be referred to as anodeless configuration.
  • the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
  • the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa or more, about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 80 MPa or more, or about 90 MPa or more.
  • the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less.
  • the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at temperatures of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C.
  • the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa (including any of the mentioned above exemplary values and/or ranges) and a temperature of about 40 °C to about 80 °C (including any of the mentioned above exemplary values and/or ranges).
  • batteries formed by the disclosed method are batteries formed by the disclosed method.
  • the as-prepared pouch cells from this dry method can be cycled at room temperature and have the potential to enable a competitive room-temperature all-solid-state lithium battery.
  • any battery configurations can be formed by the disclosed herein methods.
  • the method can be used to form coin cell batteries, pouch cell batteries, cylindrical cell batteries, and prismatic cell batteries.
  • a battery comprising: (a) a cathode electrode comprising: (i) a first substrate and (ai) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and (b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and (c) an anode electrode and wherein the battery is substantially solvent-free.
  • the cathode composite material can comprise any of the disclosed above components.
  • any of the disclosed above cathode active materials and/or the first binders can be present in the described herein battery.
  • the cathode composite material can also comprise an amount of any of the disclosed above electrolytes and/or fillers. It is understood that any of the disclosed materials can be present in any amount disclosed above.
  • the interfacial material can comprise any of the disclosed above active material and a third binder if needed. Any of the disclosed above third binders can be utilized in any of the disclosed amounts.
  • the batteries formed by the disclosed herein methods can exhibit a total impedance of less than about 1500 , less than about 1400 £1, less than about 1300 £, less than about 1200 £1, less than about 1100 , less than about 1000 £, less than about 900 , less than about 800 , less than about 700 £, less than about 600 and less than about 500 £, less than about 400 £, less than about 300 £, less than about 200 £1, less than about 100 £, less than about 50 £2, less than about 1 £2, less than about 100 m£2, less than about 50 m.Q, less than about 10 m l, or less than about 5 m£2.
  • the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg, including exemplary values of about 120 Wh/kg, about 150 Wh/kg, about 180 Wh/kg, about 200 Wh/kg, about 220 Wh/kg, about 250 Wh/kg, about 280 Wh/kg, about 300 Wh/kg, about 320 Wh/kg, about 350 Wh/kg, about 380 Wh/kg, about 400 Wh/kg, about 420 Wh/kg, about 450 Wh/kg, and about 480 Wh/kg.
  • the battery exhibits an energy density that can have any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles. In still further aspects, the battery exhibits a coulombic efficiency greater than about 80%, greater than about 85%, greater than about 90%, greater than about 92%, greater than about 95%, or greater than about 99% for at least about 100 cycles. In still further aspects, the battery exhibits a coulombic efficiency no less than about 99.9%, no less than about 99%, no less than about 95%, no less than about 92%, no less than about 90%, no less than about 85%, or no less than about 80% for at least about 100 cycles.
  • the batteries can operate at a temperature having any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values.
  • the battery can operate at a temperature of about -15 °C up to about 100 °C, about -10 °C up to about 100 °C, about -5 °C up to about 100 °C, about -15 °C up to about 90, about -15 °C up to about 60, about 0 °C up to about 100 °C, about 5 °C up to about 100 °C, about 20 °C up to about 100 °C, about 20 °C up to about 90 °C, about 20 °C up to about 80 °C, and about 20 °C up to about 70 °C, about 20 °C up to about 50 °C, about 20 °C up to about 40 °C, about 20 °C up to about 30 °C, about 25 °C up to about 55
  • Example 1 A method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
  • Example 3 The method of any one of examples herein, particularly example 1 or 2, wherein the first substrate is a first current collector.
  • Example 4 The method of any one of examples herein, particularly example 3, wherein the first current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
  • Example 6 The method of any one of examples herein, particularly examples 1 -5, wherein the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickel-manganese-cobalt oxide) cathode, NCA (nickel-cobalt- aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
  • the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based ca
  • Example 7 The method of any one of examples herein, particularly examples 1 -6, wherein the first binder comprises polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
  • Example 8 The method of any one of examples herein, particularly examples 1 -7, wherein the cathode active material and the binder are homogeneously pre-mixed to form the cathode composite material.
  • Example 19 The method of any one of examples herein, particularly example 17 or 18, wherein the second binder is present in an amount greater than 0 wt% to about 20 wt%.
  • Example 23 The method of any one of examples herein, particularly examples 1 -22, wherein the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
  • Example 24 The method of any one of examples herein, particularly examples 2-23, wherein the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), LisN, U3PS4, U3P, or a combination thereof.
  • the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
  • Example 35 The method of any one of examples herein, particularly examples 1 -34, wherein the depositing of the uniform layer of the cathode composite material and/or the uniform layer of the electrolyte material comprises doctor blade dry powder casting, melted mixing slurry coating, dry powder sprayer/coater/duster, or any combination thereof.
  • Example 49 The battery of any one of examples herein, particularly examples 40-48, wherein the cathode composite material further comprises one or more fillers.
  • Example 52 The battery of any one of examples herein, particularly examples 40-51 , wherein the active cathode material is present in an amount of about 50 wt% to less than about 100 wt%.
  • Example 57 The battery of any one of examples herein, particularly examples 40-56, wherein the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide-based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
  • the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide-based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitrid
  • Example 58 The battery of any one of examples herein, particularly examples 40-57, wherein the at least one electrolyte comprises doped and undoped zirconium oxide (LLZO, Li?La3Zr20i2), lithium aluminum titanium phosphate (LATP, Li1 4AI04Ti1 6(PO4)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.5(P04)3), lithium zirconium chloride (LZC, Li2ZrCle), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIO, LisInCle), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBI-ULil/LiBr/LiCI), and lithium carboborates (UCB11H12), xLi2S-yP2Ss, U2S — Lil — P2S5, U2S

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Abstract

Disclosed is a method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free. Also disclosed are batteries formed by the described method.

Description

MATERIALS AND METHODS FOR ALL-SOLID-STATE BATTERIES CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No.63/587, 475, filed on October 3, 2023, the contents of which are hereby incorporated in their entirety.
TECHNICAL FIELD
[0002] This application relates generally to secondary all-solid-state batteries and methods of making the same.
BACKGROUND
[0003] The urgent need for clean and renewable power and the rapid development of electric vehicles (EV) and portable electronic devices drive the strong demand for high-energy-density batteries. Lithium metal batteries (LMB) have come into the spotlight due to the specific capacity of the Li metal anode (3860 mAh g-1), which is about 10 times greater than that of the graphite anode (370 mAh g-1) employed by currently commercialized Li-ion batteries (LIBs). The origin of rechargeable lithium metal batteries dates to the 1970s. However, the safety of lithium anode is still problematic. One challenge is the uncontrollable formation of mossy and dendritic lithium metal on the anode during the charging of the cell. Li dendrites drastically reduce the lifespan of a battery and cause low Coulombic efficiency. Additionally, dendrites can lead to an internal short circuit, which can cause a catastrophic failure, resulting in a battery fire or explosion.
[0004] Compared to the traditional liquid-electrolyte lithium-ion batteries (LIBs), allsolid-state lithium batteries consisting of a solid-state electrolyte in place of a liquid electrolyte (ASSLBs) have been proven to enable higher energy density and superior safety. Among solid-state electrolyte materials, ceramic fast-ion conductors have attracted a great deal of attention owing to their superior intrinsic material properties, such as high ionic conductivity, high electrochemical stability, high thermal stability, and mechanical rigidity. However, processing these materials into such a format that they can be implemented into large format cells is an ongoing development in the industry. Typically, there are two primary methods to process ceramic electrolyte materials: a slurry coating and a dry film process. The slurry coating avenue is more compatible with the current conventional LIB production technology but has more limitations on the selection of binders and solvents due to the high reactivity of ceramic electrolytes. On the other hand, the dry film process does not involve any solvents, which is a promising approach for ASSLBs manufacturing. Currently, most of the developed dry film methods use fibrous PTFE as the binder and require a shearing mixer as well as a calendaring machine.
[0005] Thus, new approaches to forming all-solid-state batteries are needed. These needs and other needs are at least partially satisfied by the present disclosure.
SUMMARY
[0006] The present disclosure is directed to a method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
[0007] Also disclosed are aspects directed to a battery comprising: (a) a cathode electrode comprising: (i) a first substrate and (ai) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and (b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and (c) an anode electrode and wherein the battery is substantially solvent-free. [0008] Additional advantages will be set forth in part in the description that follows, and in part will be obvious from the description or can be learned by practice of the aspects described below. The advantages described below will be realized and attained by means of the chemical compositions, methods, and combinations thereof, particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and is not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF DRAWINGS
[0009] FIGURE 1 depicts the schematic diagram of the layer-by-layer solvent-free process for the all-solid-state lithium metal battery preparation.
[0010] FIGURE 2 depicts the Electrochemical Impedance Spectroscopy (EIS) Nyquist plots of the all-solid-state pouch cell with the composition of LFP/LZC/LPSCI/Li.
[0011] FIGURE 3 depicts the charge/discharge profiles of the first two cycles for the all-solid-state pouch cell with the composition of LFP/LZC/LPSCI/Li at a current rate of C/20.
[0012] The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.
DETAILED DESCRIPTION
[0013] The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present articles, systems, and/or methods are disclosed and described, it is to be understood that this invention is not limited to the specific or exemplary aspects of articles, systems, and/or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. [0014] The following description of the invention is provided as an enabling teaching of the invention in its best, currently known aspect. To this end, those skilled in the relevant art will recognize and appreciate that many changes can be made to the various aspects of the invention described herein while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the pertinent art will recognize that many modifications and adaptations to the present invention are possible and may even be desirable in certain circumstances and are a part of the present invention. Thus, the following description is again provided as illustrative of the principles of the present invention and not in limitation thereof.
DEFINITIONS
[0015] As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance can or cannot occur and that the description includes instances where said event or circumstance occurs and instances where it does not.
[0016] For the terms "for example" and "such as" and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise.
[0017] It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate aspects, can also be provided in combination in a single aspect. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single aspect, can also be provided separately or in any suitable subcombination.
[0018] As used in the description and the appended claims, the singular forms “a, “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to “a battery” includes two or more such batteries and a reference to “a substrate” includes two or more such substrates and the like.
[0019] Throughout the description and claims of this specification, the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and are not intended to exclude, for example, other additives, segments, integers, or steps. Furthermore, it is to be understood that the terms comprise, comprising, and comprises as they relate to various aspects, elements, and features of the disclosed invention also include the more limited aspects of “consisting essentially of” and “consisting of.”
[0020] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims which follow, reference will be made to a number of terms that shall be defined herein.
[0021] For the terms "for example" and "such as," and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used for explanatory purposes only. It is further understood that the term “exemplary,” as used herein, means “an example of” and is not intended to convey an indication of a preferred or ideal aspect.
[0022] The expressions "ambient temperature" and "room temperature" as used herein are understood in the art and refer generally to a temperature from about 20 °C to about 35 °C.
[0023] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values, inclusive of the recited values, may be used. Further, ranges can be expressed herein as from “about” one particular value and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint.
[0024] As used herein, the terms "about" or "approximately" when referring to a measurable value such as an amount, a percentage, and the like, are meant to encompass variations of ±20%, ±10%, ±5%, or ±1 % from the measurable value.
[0025] When a range is expressed, a further aspect includes from the one particular value and to the other particular value. For example, where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure, e.g., the phrase "x to y" includes the range from 'x' to 'y' as well as the range greater than 'x' and less than 'y'. The range can also be expressed as an upper limit, e.g., 'x, y, z, or less' and should be interpreted to include the specific ranges of ‘x,’ ‘y,’ ‘z,’ 'about x,' 'about y,' and 'about z' as well as the ranges of 'less than x,' 'less than y, or 'less than z,' or 'less than about x,' 'less than about y, and 'less than about z.' Likewise, the phrase ' x, y, z, or greater' should be interpreted to include the specific ranges of ‘x,’ ‘y,’ ‘z,’ 'about x,' 'about y ,’ and 'about z' as well as the ranges of 'greater than x,' greater than y,' 'greater than z,' or 'greater than about x,' greater than about y,' 'greater than about z.' In addition, the phrase " 'x' to 'y'," where 'x' and 'y' are numerical values, also includes "about 'x' to about 'y'."
[0026] Such a range format is used for convenience and brevity and, thus, should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of " 0.1 % to 5%" should be interpreted to include not only the explicitly recited values of 0.1 % to 5% but also include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1 .1 %; 5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range.
[0027] Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1 , 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.
[0028] In still further aspects, when the specific values are disclosed between two end values, it is understood that these end values can also be included.
[0029] In still further aspects, when the range is given, and exemplary values are provided, it is understood that any ranges can be formed between any exemplary values within the broadest range. For example, if individual numbers 1 , 2, 3, 4, 5, 6, 7, etc. are disclosed, then the ranges 1 -7, 2-7, 3-7, 4-7, 5-7, 6-7, 1 -6, 1 -5, 1 -4, 1 -3, 1 -2, 2-6, 2-5, etc. are also disclosed.
[0030] References in the specification and concluding claims to parts by weight of a particular element or component in a composition denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight, components Y, X, and Y are present at a weight ratio of 2:5 and are present in such a ratio regardless of whether additional components are contained in the mixture. [0031] A weight percent (wt.%) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.
[0032] It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element, or intervening elements may be present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationship between elements or layers should be interpreted in a like fashion (e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," "on" versus "directly on").
[0033] For the terms "for example" and "such as" and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used for explanatory purposes only. It is further understood that the term “exemplary,” as used herein, means “an example of” and is not intended to convey an indication of a preferred or ideal aspect.
[0034] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
[0035] It will be understood that although the terms "first," "second," etc., may be used herein to describe various elements, components, regions, layers, and/or sections. These elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of example embodiments. [0036] As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.
[0037] Still further, the term “substantially” can, in some aspects, refer to at least about 80 %, at least about 85 %, at least about 90 %, at least about 91 %, at least about 92 %, at least about 93 %, at least about 94 %, at least about 95 %, at least about 96 %, at least about 97 %, at least about 98 %, at least about 99 %, or about
100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount.
[0038] In other aspects, as used herein, the term “substantially free,” when used in the context of a composition or component of a composition that is substantially absent, is intended to refer to an amount that is then about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition.
[0039] It is understood that the term “salt,” as used herein, refers to a chemical compound that can be formed form a reaction between an acid and a base. It is understood that the term “salt,” as used herein, encompasses both inorganic and organic salts capable of providing the desired properties to the composition. In still further aspects, a cation of the disclosed herein salts is a metal cation.
[0040] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper," “bottom,” “top,” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the other elements or features. Thus, the term "below" can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein are interpreted accordingly.
[0041] While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only, and one of ordinary skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.
[0042] The present invention may be understood more readily by reference to the following detailed description of various aspects of the invention and the examples included therein and to the Figures and their previous and following description.
METHODS
[0043] Disclosed herein is an all-dry method to prepare films of ceramic solid electrolytes and further the All-Solid-State-Li-Batteries (ASSLBs), which involves a binder material having a low melting point as described. It is understood that the disclosed herein methods that apply to the Li-batteries can similarly be applied to Na and K- batteries, with electrolytes and cathode active materials adjusted to the presence of Na and K ions.
[0044] In some aspects, disclosed herein is a method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
[0045] In still further aspects, the first binder can comprise any polymeric material known in the art and suitable for the desired application with a melting point equal to or less than about 150 °C, equal to or less than about 140 °C, equal to or less than about 130 °C, equal to or less than about 120 °C, equal to or less than about 110 °C, equal to or less than about 100 °C, equal to or less than about 90 °C, equal to or less than about 80 °C, equal to or less than about 70 °C, equal to or less than about 60 °C, equal to or less than about 50 °C, equal to or less than about 40 °C, or equal to or less than about 30 °C. Yet in other aspects, the first binder can have a melting point equal to or greater than about 30 °C, equal to or greater than about 40 °C, equal to or greater than about 50 °C, equal to or greater than about 60 °C, equal to or greater than about 70 °C, equal to or greater than about 80 °C, equal to or greater than about 90 °C, equal to or greater than about 100 °C, equal to or greater than about 110 °C, equal to or greater than about 120 °C, equal to or greater than about 130 °C, equal to or greater than about 140 °C. In still further aspects, the first binder can have a melting point of about 30 °C to about 150 °C, including exemplary values of about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, about 120 °C, about 130 °C, and about 140 °C. It is understood that the first binder can have a melting point that falls within any two of the disclosed above values of ranges or within a range formed by any two foregoing values. For example, and without limitations, the melting point of the first binder can be about 30 °C to about 70 °C, about 40 °C to about 70 °C, about 50 °C to about 70 °C, about 60 °C to about 70 °C, about 30 °C to about 150 °C, about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on. [0046] In still further aspects, the first binder can comprise polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof. It is understood that the disclosed herein polymers are exemplary, and any polymeric materials that are suitable for the desired application and have a melting point within the disclosed range can be used. In still further aspects, it is understood that any of the disclosed herein polymers can have any molecular weight that would allow the polymer to exhibit the disclosed herein melting point.
[0047] In still further aspects, the first substrate is a first current collector. It is understood that the current collector can have any shape and size that can fit the desired application or a desired battery size. In still further aspects, the first collector can be present as a film, a sheet, a mesh, a foil, a wire, or any combination thereof.
[0048] In still further aspects, the current collector can comprise aluminum, aluminum alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, stainless steel, or any combinations and alloys thereof. It is understood that any suitable current collectors can be used to form the first substrate. Any metals or metal alloys that are suitable for use in the lithium cell can be used as current collectors.
[0049] In still further aspects, the cathode active material can comprise layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickel-manganese-cobalt oxide) cathode, NCA (nickel-cobalt-aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
[0050] Yet in still further exemplary and unlimiting aspects, the cathode active material can comprise a high density nickel-rich layered transition metal oxide (Li[NixMnyCoz]02 (x+y+z = 1 )), a lithium iron phosphate (LFP), lithium manganese oxide (LiMn2O4), or nickel-doped lithium manganese oxide (LifNio.5Mm.5jO4).
[0051] In still further aspects, in the methods disclosed herein, the cathode active material and the binder are homogeneously pre-mixed to form a homogeneous cathode composite material.
[0052] In still further aspects, the cathode composite material can comprise additional components. For example, and without limitations, in some aspects, the cathode composite material can comprise one or more fillers. In such exemplary aspects, the one or more fillers can comprise conductive fillers, flame retardants, flame-resistant agents, stabilizers, antibacterial agents, or any combination thereof. For example, and without limitations, the or more filler can comprise a carbon black, a modified carbon black, a graphene, multi-layer graphene, carbon fibers, carbon nanotubes, carbon nanospheres, graphite, a reduced graphene oxide, or any combination thereof. Yet in still further aspects, the binder present in the cathode material can comprise polyvinylidene fluoride (PVDF), polyethylene oxide), cellulose, carboxymethylcellulose (CMC), a polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), ethyl cellulose (EC), copolymers thereof, or any combination thereof.
[0053] Yet, in still further aspects, the preferable fillers are those that do not negatively affect the ionic conductivity or stability of the cathode composite material.
[0054] In still further aspects, the cathode composite material comprises an amount of the at least one electrolyte. In still further aspects, the at least one electrolyte can comprise any electrolyte commonly used in the solid Li (or Na or K) batteries. For example and without limitations, the at least one electrolyte can comprise a sulfide- based electrolyte, an oxide-based electrolyte, a halide-based electrolyte, a hydride- based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
[0055] In yet still further aspects, the at least one electrolyte can be doped and/or undoped. For example and without limitations, the at least one electrolyte can comprise doped and/or undoped zirconium oxide (LLZO, Li7LasZr20i2), lithium aluminum titanium phosphate (LATP, Lii 4Alo.4Tii.6(P04)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.5(P04)3), lithium zirconium chloride (LZC, Li2ZrCle), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIC, LisInCle), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBF Li 1/LiBr/LiCI), and lithium carboborates (UCB11 H12), xLi2S-yP2Ss, U2S — Lil — P2S5, U2S — Lil — U2O — P2S5, Li2S — LiBr — P2S5, Li2S — Li2O — P2S5, U2S — LisPO4 — P2S5, U2S — P2S5 — P2O5, Li2S — P2S5 — SiS2, U2S — P2S5 — SnS, Li2S — P2S5 — AI2S3, U2S— GeS2 or U2S— GeS2 — ZnS, LiePSsX (X=at least one of Cl, Br or I), U3PS4, U7P3S11, LiyPSe, LiBH4, U2OHCI, LisOCIo sBro.s, Na3SCIo.5(BCl4)o.5, or any combination thereof.
[0056] In still further aspects, the cathode composite material can comprise various amounts of the cathode active material, the at least one electrolyte, the first binder, and/or additional fillers or agents.
[0057] For example, and without limitations, the active cathode material can be present in an amount of about 50 wt% to less than about 100 wt%, as calculated based on a total weight of a cathode composite material. In still further aspects, the active cathode material can be present in an amount equal to or greater than about 50 wt%, equal to or greater than about 60 wt%, equal to or greater than about 70 wt%, equal to or greater than about 80 wt%, equal to or greater than about 90 wt%, or equal to or greater than about 95 wt%. Yet in other aspects, the active cathode material can be present in an amount equal to or less than about 100 wt%, equal to or less than about 90 wt%, equal to or less than about 80 wt%, equal to or less than about 70 wt%, equal to or less than about 60 wt%, or equal to or less than about 55 wt%. In still further aspects, the active cathode material is present in an amount of about 50 wt% to less than about 100 wt%, including exemplary values of about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, and about 95 wt%. It is understood that the active material can be present in any amount that falls between any of the disclosed points or ranges. For example, and without limitations, the active material can be present in an amount of about 50 wt % to about 75 wt %, or about 60 wt % to 99 wt %, or about 60 wt% to about 70 wt%, or about 65 wt % to about 85 wt % and so on. Again, it is understood that the presented values and the ranges are only exemplary, and any values or ranges can be used as they fall within the broadest range.
[0058] In still further aspects, the first binder can be present in an amount greater than 0 wt% to about 20 wt%, as calculated based on a total weight of a cathode composite material. In certain exemplary and unlimiting aspects, the first binder can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more. Yet in other aspects, the first binder can be present in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 2 wt% or less. In still further aspects, the first binder can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%. In still further aspects, the first binder can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the first binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt% to about 10 wt%, or about 3.4 wt% to about 18.7 wt%, and so on.
[0059] In still further aspects, the at least one electrolyte can be present in the cathode composite material in an amount greater than 0 wt% to about 50 wt%, as calculated based on a total weight of a cathode composite material. In still further exemplary and unlimiting aspects, the at least one electrolyte can be present in the cathode composite material in an amount greater than 0 wt%, about 5 wt% or more, about 10 wt% or more, about 15 wt% or more, about 20 wt% or more, about 25 wt% or more, about 30 wt% or more, about 35 wt% or more, about 40 wt% or more, about 45 wt% or more, about 49 wt% or more. In yet still further aspects, the at least one electrolyte can be present in the cathode composite material in an amount of about 50 wt% or less, about 45 wt% or less, about 40 wt% or less, about 35 wt% or less, about 30 wt% or less, about 25 wt% or less, about 20 wt% or less, about 15 wt% or less, about 10 wt% or less, about 5 wt% or less, about 1 wt% or less. Yet in still further aspects, the at least one electrolyte can be present in the cathode composite material in an amount greater than 0 wt% to about 50 wt%, including exemplary values of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, and about 45 wt%. In still further aspects the at least one electrolyte can be present in the cathode composite material in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the at least one electrolyte can be present in the cathode composite material in an amount in of about 1 wt% to about 45 wt%, or about 2 wt % to about 7 wt%, or about 5 wt% to about 30 wt%, and so on.
[0060] In still further aspects, the one or more fillers can be present in any amount that suits the desired application. In exemplary and unlimiting aspects, the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%, as calculated based on a total weight of a cathode composite material. For example, and without limitations, the one or more fillers can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more. Yet in other aspects, the one or more fillers can be present in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 2 wt% or less. In still further aspects, the one or more fillers can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%. In still further aspects, the one or more fillers can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the first binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt% to about 10 wt%, or about 5 wt% to about 19 wt%, and so on.
[0061] In still further aspects, in the methods disclosed herein, the cathode composite material is hot pressed into the first substrate. In such exemplary and unlimiting aspects, the cathode composite material can be hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa. For example, the cathode composite material can be hot pressed into the first substrate at a pressure of about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 80 MPa or more, or about 90 MPa or more. Yet in other aspects, the cathode composite material can be hot pressed into the first substrate at a pressure of about 100 MPa or less, about 90 MPa or less, about 80 MPa or less, about 70 MPa or less, about 60 MPa or less, about 50 MPa or less, about 40 MPa or less, about 30 MPa or less, or about 20 MPa or less. Yet in other aspects, the cathode composite material can be hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa, including exemplary values of about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, and about 90 MPa. In still further aspects, the cathode composite material can be hot pressed into the first substrate at a pressure having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the cathode composite material can be hot pressed into the first substrate at a pressure of about 10 MPa to about 80 MPa, or about 30 MPa to about 55 MPa, or about 45 MPa to about 95 MPa and so on. [0062] In some aspects, the cathode composite material can be hot pressed into the first substrate at a temperature of about 40 °C to about 80 °C. Yet in still further aspects, the cathode composite material can be hot pressed into the first substrate at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more. Yet in other aspects, the cathode composite material can be hot pressed into the first substrate at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less. Yet in other aspects, the cathode composite material can be hot pressed into the first substrate at a temperature of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C. In still further aspects, the cathode composite material can be hot pressed into the first substrate at temperatures having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the cathode composite material can be hot pressed into the first substrate at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
[0063] In still further aspects, the cathode composite material is hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa (including any of the mentioned above exemplary values and/or ranges) and a temperature of about 40 °C to about 80 °C (including any of the mentioned above exemplary values and/or ranges).
[0064] In aspects disclosed herein, the electrolyte material can further comprise a second binder having a melting point equal to or less than about 70 °C. In such aspects, the second binder can comprise any polymeric material known in the art and suitable for the desired application with a melting point equal to or less than about 150 °C, equal to or less than about 140 °C, equal to or less than about 130 °C, equal to or less than about 120 °C, equal to or less than about 110 °C, equal to or less than about 100 °C, equal to or less than about 90 °C, equal to or less than about 80 °C, equal to or less than about 70 °C, equal to or less than about 60 °C, equal to or less than about 50 °C, equal to or less than about 40 °C, or equal to or less than about 30 °C. Yet in other aspects, the second binder can have a melting point equal to or greater than about 30 °C, equal to or greater than about 40 °C, equal to or greater than about 50 °C, equal to or greater than about 60 °C, equal to or greater than about 70 °C, equal to or greater than about 80 °C, equal to or greater than about 90 °C, equal to or greater than about 100 °C, equal to or greater than about 110 °C, equal to or greater than about 120 °C, equal to or greater than about 130 °C, equal to or greater than about 140 °C. In still further aspects, the second binder can have a melting point of about 30 °C to about 150 °C, including exemplary values of about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, about 120 °C, about 130 °C, and about 140 °C. It is understood that the second binder can have a melting point that falls within any two of the disclosed above values of ranges. For example, and without limitations, the melting point of the second binder can be about 30 °C to about 70 °C, or about 40 °C to about 70 °C, or about 50 °C to about 70 °C, or about 60 °C to about 70 °C, or about 30 °C to about 150 °C, or about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on.
[0065] In still further aspects, the second binder can comprise any of the disclosed above polymer materials. In some aspects, the second binder is the same as the first binder. Yet, in other aspects, the second binder is different from the first binder.
[0066] In certain aspects, the electrolyte material can optionally comprise additional fillers and/or salts. In such aspects, the electrolyte material can comprise additional ceramic materials, additional inorganic salts, and possible polymers that are elected from any of the disclosed herein lists.
[0067] In still further aspects, the second binder is present in an amount greater than 0 wt% to about 20 wt% (as calculated based on a total weight of the electrolyte material). In certain exemplary and unlimiting aspects, the second binder can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more. Yet in other aspects, the second binder can be present in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 2 wt% or less. In still further aspects, the second binder can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%. In still further aspects, the second binder can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the second binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt % to about 10 wt%, or about 3.4 wt% to about 18.7 wt%, and so on.
[0068] In some aspects, the methods disclosed herein comprise homogeneously pre-mixing the at least one electrolyte and the second binder prior to the deposition of the uniform layer on the cathode electrode.
[0069] In some aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and 40 °C to about 80 °C. In such exemplary and unlimiting aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa. For example, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 80 MPa or more, or about 90 MPa or more. Yet in other aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 100 MPa or less, about 90 MPa or less, about 80 MPa or less, about 70 MPa or less, about 60 MPa or less, about 50 MPa or less, about 40 MPa or less, about 30 MPa or less, or about 20 MPa or less. Yet in other aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa, including exemplary values of about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, and about 90 MPa. In still further aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 80 MPa, or about 30 MPa to about 55 MPa, or about 45 MPa to about 95 MPa and so on.
[0070] In some aspects, the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 40 °C to about 80 °C. Yet in still further aspects, the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more. Yet in other aspects, the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less. Yet in other aspects, the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C. In still further aspects, the electrolyte layer is hot pressed with the cathode electrode at a temperature having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the electrolyte layer is hot pressed with the cathode electrode at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
[0071] In still further aspects, the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa (including any of the mentioned above exemplary values and/or ranges) and a temperature of about 40 °C to about 80 °C (including any of the mentioned above exemplary values and/or ranges).
[0072] In still further aspects, the methods disclosed herein can further comprise a step of forming a layer of an interfacial material disposed between the electrolyte layer and the anode electrode. In such exemplary and unlimiting aspects, the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li?La3Zr20i2 (LLZO), LisN, U3PS4, U3P, or a combination thereof. In some examples, the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
[0073] In certain aspects, the interfacial material can further comprise a third binder. It is understood that the third binder can be any of the disclosed above polymer materials having a melting point equal to or less than about 150 °C, equal to or less than about 140 °C, equal to or less than about 130 °C, equal to or less than about 120 °C, equal to or less than about 110 °C, equal to or less than about 100 °C, equal to or less than about 90 °C, equal to or less than about 80 °C, equal to or less than about 70 °C, equal to or less than about 60 °C, equal to or less than about 50 °C, equal to or less than about 40 °C, or equal to or less than about 30 °C. Yet in other aspects, the third binder can have a melting point equal to or greater than about 30 °C, equal to or greater than about 40 °C, equal to or greater than about 50 °C, equal to or greater than about 60 °C, equal to or greater than about 70 °C, equal to or greater than about 80 °C, equal to or greater than about 90 °C, equal to or greater than about 100 °C, equal to or greater than about 110 °C, equal to or greater than about 120 °C, equal to or greater than about 130 °C, equal to or greater than about 140 °C. In still further aspects, the third binder can have a melting point of about 30 °C to about 150 °C, including exemplary values of about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, about 120 °C, about 130 °C, and about 140 °C. It is understood that the third binder can have a melting point that falls within any two of the disclosed above values of ranges. For example, and without limitations, the melting point of the third binder can be about 30 °C to about 70 °C, or about 40 °C to about 70 °C, or about 50 °C to about 70 °C, or about 60 °C to about 70 °C, or about 30 °C to about 150 °C, or about 45 °C to about 145 °C, or about 67 °C to about 138 °C, and so on.
[0074] In some aspects, the third binder is the same as the first binder. Yet, in other aspects, the third binder is different from the first binder. In some aspects, the third binder is the same as the second binder. Yet, in other aspects, the third binder is different from the second binder. In some aspects, the third binder is the same as the first binder and the second binder. Yet, in other aspects, the third binder is different from the first binder and the second binder.
[0075] In still further aspects, the third binder is homogeneously pre-mixed with the active material of the interfacial material prior to forming the layer of the interfacial material.
[0076] It is understood that all pre-mixing disclosed herein can be done by any known in the art methods as long as a final mixture is homogeneously mixed.
[0077] In still further aspects, the third binder is present in an amount greater than 0 wt% to about 20 wt%, as calculated based on a total weight of the interfacial layer. In certain exemplary and unlimiting aspects, the third binder can be present in an amount greater than 0 wt%, or about 2 wt% or more, about 5 wt% or more, about 8 wt% or more, about 10 wt% or more, about 12 wt% or more, about 15 wt% or more, or about 18 wt% or more. Yet in other aspects, the third binder can be present in an amount of about 20 wt% or less, about 18 wt% or less, about 15 wt% or less, about 12 wt% or less, about 10 wt% or less, about 8 wt% or less, about 5 wt% or less, or about 2 wt% or less. In still further aspects, the third binder can be present in an amount greater than 0 wt% to about 20 wt%, including exemplary values of about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, and about 19 wt%. In still further aspects, the third binder can be present in any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the third binder can be present in an amount of about 1 wt% to about 7.5 wt%, or about 5 wt % to about 10 wt%, or about 3.4 wt% to about 19 wt%, and so on.
[0078] In some aspects, the method disclosed herein comprises hot pressing the interfacial layer with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0079] For example, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 80 MPa or more, or about 90 MPa or more. Yet in other aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 100 MPa or less, about 90 MPa or less, about 80 MPa or less, about 70 MPa or less, about 60 MPa or less, about 50 MPa or less, about 40 MPa or less, about 30 MPa or less, or about 20 MPa or less. Yet in other aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa, including exemplary values of about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, and about 90 MPa. In still further aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 80 MPa, or about 30 MPa to about 55 MPa, or about 45 MPa to about 95 MPa and so on.
[0080] In some aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C to about 80 °C. Yet in still further aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more. Yet in other aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less. Yet in other aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C. In still further aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at temperatures having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
[0081] In still further aspects, the interfacial layer can be hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa (including any of the mentioned above exemplary values and/or ranges) and a temperature of about 40 °C to about 80 °C (including any of the mentioned above exemplary values and/or ranges).
[0082] In still further aspects, the anode electrode comprises Li metal, Li-alloys, carbon-based anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof. In still further aspects, the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery. In still further aspects, the anode electrode is formed in situ on a bare current collector, where the current collector can comprise any of the disclosed herein materials. In some aspects, such a battery can be referred to as anodeless configuration.
[0083] In certain aspects, the method comprises depositing Li on a second substrate to form an anode electrode. Yet, in other aspects, the anode electrode comprises a second substrate that Li metal is deposited upon. In still further aspects, the second substrate is a second current collector. In such exemplary and unlimiting aspects, the second current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
[0084] In still further aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0085] For example, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa or more, about 10 MPa or more, about 20 MPa or more, about 30 MPa or more, about 40 MPa or more, about 50 MPa or more, about 60 MPa or more, about 70 MPa or more, about 80 MPa or more, or about 90 MPa or more. Yet in other aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 100 MPa or less, about 90 MPa or less, about 80 MPa or less, about 70 MPa or less, about 60 MPa or less, about 50 MPa or less, about 40 MPa or less, about 30 MPa or less, or about 20 MPa or less, or about 10 MPa or less. Yet in other aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure ofO MPa to about 100 MPa, including exemplary values of about 10 MPa, about 20 MPa, about 30 MPa, about 40 MPa, about 50 MPa, about 60 MPa, about 70 MPa, about 80 MPa, and about 90 MPa. In still further aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 0 MPa to about 15 MPa, or about 5 MPa to about 10 MPa, or about 1 MPa to about 25 MPa or about 5 MPa to about 50 MPa and so on.
[0086] In some aspects, the anode electrode is hot pressed with the electrolyte layer, and the cathode electrode has a temperature of about 40 °C to about 80 °C. Yet in still further aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 40 °C or more, about 45 °C or more, about 50 °C or more, about 55 °C or more, about 60 °C or more, about 65 °C or more, about 70 °C or more, or about 75 °C or more. Yet in other aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 80 °C or less, about 75 °C or less, about 70 °C or less, about 65 °C or less, about 60 °C or less, about 55 °C or less, about 50 °C or less, or about 45 °C or less. Yet in other aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at temperatures of about 40 °C to about 80 °C, including exemplary values of about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, and about 75 °C. In still further aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at temperatures having any amount that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a temperature of about 45 °C to about 65 °C, or about 50 °C to about 75 °C, or about 40 °C to about 60 °C and so on.
[0087] In still further aspects, the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa (including any of the mentioned above exemplary values and/or ranges) and a temperature of about 40 °C to about 80 °C (including any of the mentioned above exemplary values and/or ranges).
[0088] In still further aspects, the depositing of the uniform layer of the cathode composite material and/or the uniform layer of the electrolyte material can comprise any known in the art methods suitable for the desired application. For example, the depositing of the uniform layer of the cathode composite material and/or the uniform layer of the electrolyte material can comprise doctor blade dry powder casting, melted mixing slurry coating, dry powder sprayer/coater/duster, or any combination thereof.
BATTERIES
[0089] In still further aspects, disclosed herein are batteries formed by the disclosed method. The as-prepared pouch cells from this dry method can be cycled at room temperature and have the potential to enable a competitive room-temperature all-solid-state lithium battery. It is understood that any battery configurations can be formed by the disclosed herein methods. For example, the method can be used to form coin cell batteries, pouch cell batteries, cylindrical cell batteries, and prismatic cell batteries.
[0090] In aspects disclosed herein, disclosed is a battery comprising: (a) a cathode electrode comprising: (i) a first substrate and (ai) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and (b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and (c) an anode electrode and wherein the battery is substantially solvent-free.
[0091] In yet still further aspects, the battery further comprises a layer of an interfacial material disposed between the electrolyte layer and the anode electrode.
[0092] It is understood that the cathode composite material can comprise any of the disclosed above components. In other words, any of the disclosed above cathode active materials and/or the first binders can be present in the described herein battery. In still further aspects, and as disclosed above, the cathode composite material can also comprise an amount of any of the disclosed above electrolytes and/or fillers. It is understood that any of the disclosed materials can be present in any amount disclosed above.
[0093] In some aspects, the electrolytes can comprise any of the disclosed above electrolytes without any limitations. In still further aspects, the electrolyte material can also comprise any of the disclosed above second binders. It is understood that all the components can be present in any of the disclosed above amounts.
[0094] Still further, the interfacial material can comprise any of the disclosed above active material and a third binder if needed. Any of the disclosed above third binders can be utilized in any of the disclosed amounts.
[0095] In still further aspects, the anode electrode can comprise any of the disclosed above materials. If the anode electrode comprises a second substrate comprising a second current collector, such a current collector can be chosen from any disclosed above collectors.
[0096] In still further aspects, the batteries formed by the disclosed herein methods can exhibit a total impedance of less than about 1500 , less than about 1400 £1, less than about 1300 £1, less than about 1200 £1, less than about 1100 , less than about 1000 £1, less than about 900 , less than about 800 , less than about 700 £1, less than about 600 and less than about 500 £1, less than about 400 £1, less than about 300 £1, less than about 200 £1, less than about 100 £2, less than about 50 £2, less than about 1 £2, less than about 100 m£2, less than about 50 m.Q, less than about 10 m l, or less than about 5 m£2. In still further aspects, the batteries formed by the disclosed herein methods can exhibit a total impedance not greater than about 5 m.Q, not greater than about 10 mQ, not greater than about 50 mQ, not greater than about 100 mP., not greater than about 1 £2, not greater than about 50 £2, not greater than about 100 £2, not greater than about 200 £2, not greater than about 300 £2, not greater than about 400 £1, not greater than about 500 £2, not greater than about 600 £2, not greater than about 700 £2, not greater than about 800 £1, not greater than about 900 £2, not greater than about 1000 £2, not greater than about 1100 £2, not greater than about 1200 £2, not greater than about 1300 £2, or not greater than about 1400 £2. Yet in still further aspects, the batteries formed by the disclosed herein methods can exhibit a total impedance of about 1 m£2 to about 1500 £2, including exemplary values of about 10 m.Q, about 50 mQ, about 100 m.Q, about 1 £2, about 50 £2, about 100 £2, about 200 £2, about 300 £2, about 400 £2, about 500 £2, about 600 £2, about 700£2, about 800 £2, about 900 £2, about 1000 £2, about 1 100 £2, about 1200 £2, about 1300 £2, and about 1400 £2. In still further aspects, the batteries formed by the disclosed herein methods can exhibit a total impedance having any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the batteries formed by the disclosed herein methods can exhibit a total impedance of about 1 m£2 to about 1 £2, about 1 £2 to about 100 £2, about 500 £2 to about 1500 £2, or about 500 £1 to about 1400 £2, or about 500 £1 to about 1300 £2, or about 500 £2 to about 1200 £2, or about 500 £1 to about 1100 £1, or about 500 £1 to about 1000 £2, or about 650 £1 to about 1500 £2, or about 650 £1 to about 1300 £2, or about 650 £1 to about 1000 £2, or about 750 £1 to about 1100 £1, and so on.
[0097] In still further aspects, the disclosed herein battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg. In still further aspects, the battery exhibits an energy density of about 100 Wh/kg or more, about 150 Wh/kg or more, about 200 Wh/kg or more, about 250 Wh/kg or more, about 300 Wh/kg or more, about 350 Wh/kg or more, about 400 Wh/kg or more, or about 450 Wh/kg or more. In still further aspects, the battery exhibits an energy density of about 500 Wh/kg or less, about 450 Wh/kg or less, about 400 Wh/kg or less, about 350 Wh/kg or less, about 300 Wh/kg or less, about 250 Wh/kg or less, about 200 Wh/kg or less, or about 150 Wh/kg or less. In still further aspects, the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg, including exemplary values of about 120 Wh/kg, about 150 Wh/kg, about 180 Wh/kg, about 200 Wh/kg, about 220 Wh/kg, about 250 Wh/kg, about 280 Wh/kg, about 300 Wh/kg, about 320 Wh/kg, about 350 Wh/kg, about 380 Wh/kg, about 400 Wh/kg, about 420 Wh/kg, about 450 Wh/kg, and about 480 Wh/kg. In still further aspects, the battery exhibits an energy density that can have any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg, about 150 Wh/kg to about 500 Wh/kg, about 200 Wh/kg to about 500 Wh/kg, about 100 Wh/kg to about 400 Wh/kg, about 100 Wh/kg to about 300 Wh/kg, 100 Wh/kg to about 250 Wh/kg, and so on.
[0098] In still further aspects, the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g when discharged at about 0.1 C to about 10C rate. In yet other aspects, the battery exhibits a specific discharge capacity of about 50 mA h/g or more, about 75 mA h/g or more, about 100 mA h/g or more, about 120 mA h/g or more, about 150 mA h/g or more, about 175 mA h/g or more, about 200 mA h/g or more, about 225 mA h/g or more, about 250 mA h/g or more, about 275 mA h/g or more. Yet in other aspects, the battery exhibits a specific discharge capacity of about 300 mA h/g or less, about 275 mA h/g or less, about 250 mA h/g or less, about 225 mA h/g or less, about 200 mA h/g or less, about 175 mA h/g or less, about 150 mA h/g or less, about 125 mA h/g or less, about 100 mA h/g or less, or about 75 mA h/g or less. In still further aspects, the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g, including exemplary values of about 50 mA h/g, about 75 mA h/g, about 100 mA h/g, about 125 mA h/g, about 150 mA h/g, about 175 mA h/g, about 200 mA h/g, about 225 mA h/g, about 250 mA h/g, and about 275 mA h/g. In still further aspects, the battery exhibits a specific discharge capacity that can have any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g, about 50 mA h/g to about 200 mA h/g, about 50 mA h/g to about 100 mA h/g, about 75 mA h/g to about 300 mA h/g, about 100 mA h/g to about 300 mA h/g, and so on. In still further aspects, the battery exhibits the disclosed above specific discharge capacity when discharged at about 0.05C to about 20C rate. In such aspects, the discharge rate can be about 0.1 C, about 0.2C, about 0.3C, about 0.4C, about 0.5C, about 1 C, about 2C, about 4G, about 5C, about 6C, about 7C, about 8C, about 9 C, about 10 C, about 11 C, about 12 C, about 13 C, about 14 C, about 15 C, about 16 C, about 17 C, about 18 C, and about 19 C. In still further aspects, the discharge rate can have any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the discharge rate can be about 0.05C to about 20C rate, about 0.1 C to about 20C rate, about 0.1 C to about 10C, about 0.5C to about 20C rate, rate about 0.2C to about 10C rate, about 0.5C to about 8C rate, about 2C to about 10C rate, about 4C to about 10C rate and so on.
[0099] In still further aspects, the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles. In still further aspects, the battery exhibits a coulombic efficiency greater than about 80%, greater than about 85%, greater than about 90%, greater than about 92%, greater than about 95%, or greater than about 99% for at least about 100 cycles. In still further aspects, the battery exhibits a coulombic efficiency no less than about 99.9%, no less than about 99%, no less than about 95%, no less than about 92%, no less than about 90%, no less than about 85%, or no less than about 80% for at least about 100 cycles. In still further aspects, the coulombic efficiency can be in a range of about 80% to about 100%, including exemplary values of about 85%, about 90%, about 95%, about 99%, and about 99.99% for at least 100 cycles. In still further aspects, the coulombic efficiency can have any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, the coulombic efficiency can be about 80% to about 100%, or about 80 to about 99%, or about 80% to about 95%, and so on. In still further aspects, such a coulombic efficiency can be demonstrated for at least about 100 cycles, or for about 100 cycles or more, for about 200 cycles or more, for about 500 cycles or more, for about 1000 cycles or more, for about 2000 cycles or more, for about 5000 cycles or more, 10000 for about 100 cycles or more, or even 100000 or more.
[0100] In still further aspects, the batteries disclosed herein are configured to operate in a temperature range from about -20 °C up to about 100 °C, including exemplary values of about -15 °C, about -10 °C, about -5 °C, about 0 °C, about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, about 85 °C, about 90 °C, and about 95 °C. In still further aspects, the batteries can operate at a temperature having any value that falls between any two foregoing values, or it can be present in any range that is formed by any of the foregoing values. For example, and without limitations, the battery can operate at a temperature of about -15 °C up to about 100 °C, about -10 °C up to about 100 °C, about -5 °C up to about 100 °C, about -15 °C up to about 90, about -15 °C up to about 60, about 0 °C up to about 100 °C, about 5 °C up to about 100 °C, about 20 °C up to about 100 °C, about 20 °C up to about 90 °C, about 20 °C up to about 80 °C, and about 20 °C up to about 70 °C, about 20 °C up to about 50 °C, about 20 °C up to about 40 °C, about 20 °C up to about 30 °C, about 25 °C up to about 55 °C, about 30 °C up to about 85 °C and so on.
[0101] In still further aspects, the rechargeable batteries that comprise the disclosed herein electrolytes and separators exhibit exceptional performance over hundreds of plating/stripping cycles. In still further aspects, the anode in the disclosed herein batteries is substantially free of dendrites during a plating/stripping cycle of a battery operation.
[0102] Yet in still further aspects, the ceramic layer disposed on the first surface of the substrate is substantially free of dendrites during a plating/stripping cycle of a battery operation.
[0103] In some exemplary and unlimiting aspects, disclosed herein is a rechargeable battery comprising: a Li anode material, a cathode material, and an electrolyte, wherein the electrolyte comprises about 1 M to about 4 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DMI.
[0104] In such aspects, the electrolytes comprise about 1 M to about 4 M, including exemplary values of about 1 .1 M, about 1 .2 M, about 1 .3 M, about 1 .4 M, about 1 .5 M, about 1 .6 M, about 1 .7 M, about 1 .8 M, about 1 .9 M, about 2 M, about 2.1 M, about 2.2 M, about 2.3 M, about 2.4 M, about 2.5 M, about 2.6 M, about 2.7 M, about 2.8 M, about 2.9 M, about 3 M, about 3.1 M, about 3.2 M, about 3.3 M, about 3.4 M, about 3.5 M, about 3.6 M, about 3.7 M, about 3.8 M, and about 3.9 M of lithium bis(fluorosulfonyl)imide and about 0.05 M to about 0.5 M, including exemplary values of about 0.06 M, about 0.07 M, about 0.08 M, about 0.09 M, about 0.1 M, about 0.15 M, about 0.2 M, about 0.25 M, about 0.3 M, about 0.35 M, about 0.4 M, and about 0.45 M of lithium difluoro(oxalato)borate dissolved in a mixture of solvents comprising about 40 vol% to about 90 vol% of DME, about 10 vol% to about 60 vol% of DOL, and about 0.05 wt% to about 5 wt% of DM I. In such exemplary aspects, the mixture of solvents can comprise about 40 vol% to about 90 vol% of DME, including exemplary values of about 45 vol%, about 50 vol%, about 55 vol%, about 60 vol%, about 65 vol%, about 70 vol%, about 75 vol%, about 80 vol%, and about 85 vol%. In such exemplary aspects, the mixture of solvents can comprise about 10 vol% to about 60 vol% of DOL, including exemplary values of about 15 vol%, about 20 vol%, about 25 vol%, about 30 vol%, about 35 vol%, about 40 vol%, about 45 vol%, about 50 vol%, and about 55 vol%. In still further aspects, the mixture of solvents can comprise about 0.05 wt% to about 5 wt% of DMI, including exemplary values of about 0.1 wt %, about 0.25 wt %, about 0.5 wt %, about 0.75 wt %, about 1 wt %, about 1 .2 wt %, about 1 .5 wt %, about 1 .7 wt %, about 2 wt %, about 2.2 wt %, about 2.5 wt %, about 2.7 wt %, about 3 wt %, about 3.2 wt %, about 3.5 wt %, about 3.7 wt %, about 4 wt %, about 4.2 wt %, about 4.5 wt %, and about 4.7 wt % of DMI based on the total weight of the electrolyte.
[0105] In still further aspects, such rechargeable batteries can compromise a cathode comprising a high density nickel-rich layered transition metal oxide, a lithium iron phosphate (LFP), Lithium manganese oxide (LiMn2O4), or nickel doped lithium manganese oxide (Li[Nio.5Mm.5]04).
[0106] In still further aspects, such batteries can comprise a separator with any of the disclosed coatings. Yet in other aspects, such an exemplary battery having the disclosed above electrolyte system and the cathode can comprise a separator that is substantially free of the disclosed herein ceramic layer. In still further aspects, such an exemplary battery having the disclosed above electrolyte system and the cathode can comprise any commercially available separator.
[0107] In still further aspects, any of the disclosed herein batteries exhibit an energy density of about 150 Wh/kg to about 500 Wh/kg, including exemplary values of about 160 Wh/kg, about 170 Wh/kg, about 180 Wh/kg, about 190 Wh/kg, about 200 Wh/kg, about 210 Wh/kg, about 220 Wh/kg, about 230 Wh/kg, about 240 Wh/kg, about 250 Wh/kg, about 260 Wh/kg, about 270 Wh/kg, about 280 Wh/kg, about 290 Wh/kg, about 300 Wh/kg, about 310 Wh/kg, about 320 Wh/kg, about 330 Wh/kg, about 340 Wh/kg, about 350 Wh/kg, about 360 Wh/kg, about 370 Wh/kg, about 380 Wh/kg, about 390 Wh/kg, about 400 Wh/kg, about 410 Wh/kg, about 420 Wh/kg, about 430 Wh/kg, about 440 Wh/kg, about 450 Wh/kg, about 460 Wh/kg, about 470 Wh/kg, about 480 Wh/kg, and about 490 Wh/kg.
[0108] In still further aspects, any of the disclosed herein batteries exhibit a specific discharge capacity of about 100 mA h/g to about 400 mA h/g, including exemplary values of about 1 10 mA h/g, about 120 mA h/g, about 130 mA h/g, about 140 mA h/g, about 150 mA h/g, about 160 mA h/g, about 170 mA h/g, about 180 mA h/g, about 190 mA h/g, about 200 mA h/g, about 210 mA h/g, about 220 mA h/g, about 230 mA h/g, about 240 mA h/g, about 250 mA h/g, about 260 mA h/g, about 270 mA h/g, about 280 mA h/g, about 290 mA h/g, about 300 mA h/g, about 310 mA h/g, about 320 mA h/g, about 330 mA h/g, about 340 mA h/g, about 350 mA h/g, about 360 mA h/g, about 370 mA h/g, about 380 mA h/g, about 390 mA h/g when discharged at 0.1 C to 10C rate, including exemplary values of 0.2C, 0.5C, 1 C, 2C, 3C, 4C, 5C, 6C, 7C, 8C, and 9C rate.
[0109] In still further aspects, any of the disclosed herein batteries exhibit a capacity retention of at least about 80%, or at least about 81 %, or at least about 82%, or at least about 83%, or at least about 84%, or at least about 85%, or at least about 86%, or at least about 87%, or at least about 88%, or at least about 89%, or at least about 90%, or at least about 91 %, or at least about 92%, or at least about 93%, or at least about 94%, or at least about 95%, or at least about 96%, or at least about 97%, or at least about 98%, or at least about 99% for at least about 150 cycles. In still further aspects, the batteries disclosed herein exhibit the disclosed properties for at least about 200 cycles, or at least about 250 cycles, or at least about 500 cycles, or at least about 1000 cycles, or even at least about 5000 cycles.
[0110] Also disclosed herein are systems comprising one or more of any of the disclosed herein batteries. For example, the system can comprise at least about 2, at least about 5, at least about 10, at least about 50, at least about 100, at least about 500 or at least about 1000 batteries.
[0111] Also disclosed herein are articles that can comprise the disclosed herein batteries or systems. For example, the article can comprise a vehicle (land, marine, air, or space-adapted vehicles), a hand-held device, a wearable electronic device, stationary electronic devices, electrical tools, toys, energy storage devices, and the like.
[0112] By way of a non-limiting illustration, examples of certain aspects of the present disclosure are given below.
EXAMPLES
[0113] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods claimed herein are made and evaluated and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is degrees C or is at ambient temperature, and pressure is at or near atmospheric.
EXAMPLE 1
[0114] An all-solid-state pouch cell consisting of a lithium iron phosphate (LiFePC , LFP) cathode, lithium zirconium chloride (Li2ZrCle, LZC) solid-state electrolyte, lithium phosphorus sulfur chloride (LiePSsCI, LPSCI) interfacial material, and lithium metal anode has been fabricated with a novel layer-by-layer solvent-free method without specific mixing and/or a calendaring process. Polyethylene Glycol 20,000 (PEG- 20,000) was selected to demonstrate this novel all-solid-state battery fabrication process owing to its low melting point of ~60 °C. A hot-press machine was used to process the films. The as-prepared pouch cell was further evaluated for cycling performance at room temperature to prove its potential for enabling practical all-solid- state pouch cells.
[0115] All-solid-state pouch cells were produced by a disclosed herein solvent-free dry method. In this example, a low melting point (60 °C) binder, PEG-20,000, has been used combined with the hot press to prepare the LFP cathode, LZC SSE layer, and LPSCI-protected lithium metal anode. A similar method was used to prepare all-solid- state pouch cells with Li-alloy-based anodes, for example, Li-ln alloy anode. Figure 1 shows the schematic diagram of the All-Solid-State-Li-Battery (ASSLB) preparation process by the disclosed herein layer-by-layer dry method. Firstly, the fully mixed powders of LFP cathode, LZC electrolyte, PEG-20,000, and conductive carbon (70:30:5:5 wt) were uniformly sprinkled on the aluminum current collector. Then, the cathode was obtained by hot-pressing with a 50 MPa pressure at 60 °C. The PEG- 20,000 powders melt at 60 °C to bind all the cathode mixture with each other as well as the current collector. The LZC electrolyte layer (5 wt% PEG-20,000) and LPSCI interfacial layer (5 wt% PEG-20,000) were prepared step by step via the same conditions of a 50 MPa pressure and 60 °C hot-pressing. At last, the copper foil- supported lithium metal anode was pressed onto the LPSCI layer with the same temperature of 60 °C but at a lower pressure of 10 MPa, considering the softness and ductility of Li metal. The final 5-layer stack was welded electrode leads and sealed in the Mylar pouch as the regular pouch cell building process.
[0116] The as-prepared ASSLB pouch cell was rested for at least 12 hours in a testing jig that is able to provide a stable pressure as high as 10 MPa during the cell testing. After the 12 hours of stabilization, the electrochemical impedance spectra (E IS) analysis was conducted for the dry method ASSLB pouch cell. A Bio-Logic VSP instrument was used to record the EIS data over a frequency range of 1 MHz to 1 Hz with a perturbation amplitude of 10 mV. Figure 2 shows the EIS data of the dry method ASSLB pouch cell in Nyquist plots, which exhibit a semicircle in the high frequency and a sloped straight line in the low frequency. Generally, the diameter of the semicircle is related to the charge-transfer process occurring at the electrode/electrolyte interface and is in direct proportion to the impedance, including electrolyte resistance (Re), surface film resistance (Rst), and charge transfer resistance (Ret). The inclined line in the low-frequency range corresponds to the Warburg impedance (Zw) associated with the lithium-ion diffusion process inside the cell, and the slope of the straight line is in inverse proportion to the Zw. As shown in Figure 2, the total impedance of the dry method ASSLB pouch cell is about 1 ,100 Q, which is much lower than most of the reported solid-state batteries. On the other hand, the long straight line with a slope larger than 45° represents the rapid lithium-ion diffusion in the cell, as fast as that in liquid electrolyte batteries, demonstrating that the efficient allsolid-state battery can be obtained by the disclosed herein methods.
[0117] Figure 3 shows the charge/discharge profiles of the initial two cycles for the disclosed dry method LFP/LZC/LPSCI/Li pouch cell at C/20 under room temperature with a testing pressure of 10 MPa. The cell shows a relatively higher over-potential than liquid electrolyte batteries since the cell impedance is higher than normal LIBs. An initial charge capacity of 161 .25 mAh/g and Coulombic efficiency of 74.9% were achieved from the ASSLB pouch cell, which is competitive with other reported data for solid-state batteries.
EXEMPLARY ASPECTS
[0118] In view of the described electrode materials, batteries, and methods and variations thereof, herein below are described certain more particularly described aspects of the inventions. The particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulas literally used therein.
[0119] Example 1 . A method of forming an all-solid-state battery comprising: (a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; (b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and (c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
[0120] Example 2. The method of any one of examples herein, particularly example 1 , further comprises a step of forming a layer of an interfacial material disposed between the electrolyte layer and the anode electrode.
[0121] Example 3. The method of any one of examples herein, particularly example 1 or 2, wherein the first substrate is a first current collector.
[0122] Example 4. The method of any one of examples herein, particularly example 3, wherein the first current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
[0123] Example 5. The method of any one of examples herein, particularly example 3 or 4, wherein the current collector comprises aluminum, aluminum alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, stainless steel, or any combinations and alloys thereof.
[0124] Example 6. The method of any one of examples herein, particularly examples 1 -5, wherein the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickel-manganese-cobalt oxide) cathode, NCA (nickel-cobalt- aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
[0125] Example 7. The method of any one of examples herein, particularly examples 1 -6, wherein the first binder comprises polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
[0126] Example 8. The method of any one of examples herein, particularly examples 1 -7, wherein the cathode active material and the binder are homogeneously pre-mixed to form the cathode composite material.
[0127] Example 9. The method of any one of examples herein, particularly examples 1 -8, wherein the cathode composite material comprises an amount of the at least one electrolyte.
[0128] Example 10. The method of any one of examples herein, particularly examples 1 -9, wherein the cathode composite material further comprises one or more fillers.
[0129] Example 11 . The method of any one of examples herein, particularly example 10, wherein the one or more fillers comprise conductive fillers, flame retardants, flame-resistant agents, stabilizers, antibacterial agents, or any combination thereof.
[0130] Example 12. The method of any one of examples herein, particularly examples 1 -11 , wherein the cathode composite material is hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0131] Example 13. The method of any one of examples herein, particularly examples 1 -12, wherein the active cathode material is present in an amount of about 50 wt% to less than 100 wt%. [0132] Example 14. The method of any one of examples herein, particularly examples 1 -13, wherein the first binder is present in an amount greater than 0 wt% to about 20 wt%.
[0133] Example 15. The method of any one of examples herein, particularly examples 9-14, wherein the amount of the at least one electrolyte present in the cathode composite material is greater than 0 wt% to about 50 wt%.
[0134] Example 16. The method of any one of examples herein, particularly examples 10-15, wherein the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%.
[0135] Example 17. The method of any one of examples herein, particularly examples 1 -16, wherein the electrolyte material further comprises a second binder having a melting point equal to or less than about 70 °C.
[0136] Example 18. The method of any one of examples herein, particularly example 17, wherein the second binder is the same or different as the first binder.
[0137] Example 19. The method of any one of examples herein, particularly example 17 or 18, wherein the second binder is present in an amount greater than 0 wt% to about 20 wt%.
[0138] Example 20. The method of any one of examples herein, particularly examples 1 -19, wherein the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide-based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
[0139] Example 21 . The method of any one of examples herein, particularly examples 1 -20, wherein the at least one electrolyte comprises doped and undoped zirconium oxide (LLZO, Li?La3Zr20i2), lithium aluminum titanium phosphate (LATP, Lii.4Alo.4Tii.6(P04)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.5(P04)3), lithium zirconium chloride (LZC, Li2ZrCle), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIC, LisInCle), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBI-ULil/LiBr/LiCI), and lithium carboborates (UCB11H12), xLi2S-y 2Ss, Li2S— Lil— P2S5, U2S — Lil — U2O — P2S5, U2S — LiBr — P2S5, Li2S — Li2O — P2S5, Li2S — U3PO4 — P2S5, U2S — P2S5 — P2O5, Li2S — P2S5 — SiS2, Li2S — P2S5 — SnS, U2S — P2S5 — AI2S3, U2S — GeS2 or U2S — GeS2 — ZnS, LiePSsX (X=at least one of Cl, Br or I), U3PS4, U7P3S11, U7PS6, LiBFL, U2OHCI, LisOCIosBro s, Na3SCIo.5(BCl4)o.5, or any combination thereof.
[0140] Example 22. The method of any one of examples herein, particularly examples 17-21 , wherein the at least one electrolyte and the second binder are homogeneously pre-mixed prior to the deposition of the uniform layer.
[0141] Example 23. The method of any one of examples herein, particularly examples 1 -22, wherein the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0142] Example 24. The method of any one of examples herein, particularly examples 2-23, wherein the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), LisN, U3PS4, U3P, or a combination thereof. In some examples, the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
[0143] Example 25. The method of any one of examples herein, particularly example 24, wherein the interfacial material further comprises a third binder.
[0144] Example 26. The method of any one of examples herein, particularly example 25, wherein the third binder is the same or different from the first binder and/or the second binder, if present.
[0145] Example 27. The method of any one of examples herein, particularly examples 25 and 26, wherein the third binder is homogeneously pre-mixed with the active material of the interfacial material prior to forming the layer of the interfacial material.
[0146] Example 28. The method of any one of examples herein, particularly examples 25-27, wherein the third binder is present in an amount greater than 0 wt% to about 20 wt%.
[0147] Example 29. The method of any one of examples herein, particularly examples 2-28, the interfacial layer is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0148] Example 30. The method of any one of examples herein, particularly examples 1 -29, wherein the anode electrode comprises Li metal, Li-alloys, carbonbased anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof.
[0149] Example 31 . The method of any one of examples herein, particularly examples 1 -30, wherein the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery.
[0150] Example 32. The method of any one of examples herein, particularly examples 1 -30, the method comprises depositing Li on a second substrate to form an anode electrode.
[0151] Example 33. The method of any one of examples herein, particularly example 32, wherein the second substrate is a second current collector and wherein the second current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
[0152] Example 34. The method of any one of examples herein, particularly examples 1 -33, wherein the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0153] Example 35. The method of any one of examples herein, particularly examples 1 -34, wherein the depositing of the uniform layer of the cathode composite material and/or the uniform layer of the electrolyte material comprises doctor blade dry powder casting, melted mixing slurry coating, dry powder sprayer/coater/duster, or any combination thereof.
[0154] Example 36. The method of any one of examples herein, particularly examples 1 -35, wherein the battery exhibits a total impedance of less than about 1500 at room temperature.
[0155] Example 37. The method of any one of examples herein, particularly examples 1 -36, wherein the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg.
[0156] Example 38. The method of any one of examples herein, particularly examples 1 -37, wherein the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g when discharged at 0.1 C to 10C rate.
[0157] Example 39. The method of any one of examples herein, particularly examples 1 -38, wherein the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles.
[0158] Example 40. A battery comprising: (a) a cathode electrode comprising: (i) a first substrate and (ai) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and (b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and (c) an anode electrode and wherein the battery is substantially solvent-free. [0159] Example 41 . The battery of any one of examples herein, particularly example 40, wherein the battery further comprises a layer of an interfacial material disposed between the electrolyte layer and the anode electrode.
[0160] Example 42. The battery of any one of examples herein, particularly example 40 or 41 , wherein the first substrate is a first current collector.
[0161] Example 43. The battery of any one of examples herein, particularly example 42, wherein the first current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
[0162] Example 44. The battery of any one of examples herein, particularly example 42 or 43, wherein the current collector comprises aluminum, aluminum alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, stainless steel, or any combinations and alloys thereof.
[0163] Example 45. The battery of any one of examples herein, particularly examples 40-44, wherein the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickel-manganese-cobalt oxide) cathode, NCA (nickel-cobalt- aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
[0164] Example 46. The battery of any one of examples herein, particularly examples 40-45, wherein the first binder and/or second binder comprise polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
[0165] Example 47. The battery of any one of examples herein, particularly examples 40-46, wherein the cathode active material and the binder are homogeneously pre-mixed to form the cathode composite material. [0166] Example 48. The battery of any one of examples herein, particularly examples 40-47, wherein the cathode composite material comprises an amount of the at least one electrolyte.
[0167] Example 49. The battery of any one of examples herein, particularly examples 40-48, wherein the cathode composite material further comprises one or more fillers.
[0168] Example 50. The battery of any one of examples herein, particularly example 49, wherein the one or more fillers comprise conductive fillers, flame retardants, flame-resistant agents, stabilizers, antibacterial agents, or any combination thereof.
[0169] Example 51 . The battery of any one of examples herein, particularly examples 40-50, wherein the cathode composite material is hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0170] Example 52. The battery of any one of examples herein, particularly examples 40-51 , wherein the active cathode material is present in an amount of about 50 wt% to less than about 100 wt%.
[0171] Example 53. The battery of any one of examples herein, particularly examples 40-52, wherein the first binder is present in an amount greater than 0 wt% to about 20 wt%.
[0172] Example 54. The battery of any one of examples herein, particularly examples 40-53, wherein the amount of the at least one electrolyte present in the cathode composite material is greater than 0 wt% to about 50 wt%.
[0173] Example 55. The battery of any one of examples herein, particularly examples 49-54, wherein the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%. [0174] Example 56. The battery of any one of examples herein, particularly examples 40-55, wherein the second binder is present in an amount greater than 0 wt% to about 20 wt%.
[0175] Example 57. The battery of any one of examples herein, particularly examples 40-56, wherein the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide-based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
[0176] Example 58. The battery of any one of examples herein, particularly examples 40-57, wherein the at least one electrolyte comprises doped and undoped zirconium oxide (LLZO, Li?La3Zr20i2), lithium aluminum titanium phosphate (LATP, Li1 4AI04Ti1 6(PO4)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.5(P04)3), lithium zirconium chloride (LZC, Li2ZrCle), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIO, LisInCle), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBI-ULil/LiBr/LiCI), and lithium carboborates (UCB11H12), xLi2S-yP2Ss, U2S — Lil — P2S5, U2S — Lil — U2O — P2S5, U2S — LiBr — P2S5, Li2S — Li2O — P2S5, Li2S — U3PO4 — P2S5, U2S — P2S5 — P2O5, Li2S — P2S5 — SiS2, Li2S — P2S5 — SnS, U2S — P2S5 — AI2S3, U2S — GeS2 or U2S — GeS2 — ZnS, LiePSsX (X=at least one of Cl, Br or I), U3PS4, U7P3S11, LiyPSe, LiBFL, Li2OHCI, LisOCIo.sBro.s, Na3SCIo.5(BCl4)o.5, or any combination thereof
[0177] Example 59. The battery of any one of examples herein, particularly examples 40-58, wherein the at least one electrolyte and the second binder are homogeneously pre-mixed.
[0178] Example 60. The battery of any one of examples herein, particularly examples 40-59, wherein the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C. [0179] Example 61 . The battery of any one of examples herein, particularly examples 41 -60, wherein the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li?La3Zr20i2 (LLZO), LisN, U3PS4, U3P, or a combination thereof. In some examples, the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
[0180] Example 62. The battery of any one of examples herein, particularly example 61 , wherein the interfacial material further comprises a third binder.
[0181] Example 63. The battery of any one of examples herein, particularly example 62, wherein the third binder is the same or different from the first binder and/or second binder.
[0182] Example 64. The battery of any one of examples herein, particularly examples 62 and 63, wherein the third binder is homogeneously pre-mixed with the active material of the interfacial material prior to forming the layer of the interfacial material.
[0183] Example 65. The battery of any one of examples herein, particularly examples 62-64, wherein the third binder is present in an amount greater than 0 wt% to about 20 wt%.
[0184] Example 66. The battery of any one of examples herein, particularly examples 40-64, the interfacial layer is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0185] Example 67. The battery of any one of examples herein, particularly examples 40-66, wherein the anode electrode comprises Li metal, Li-alloys, carbonbased anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof. [0186] Example 68. The battery of any one of examples herein, particularly examples 40-67, wherein the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery.
[0187] Example 69. The battery of any one of examples herein, particularly examples 40-67, wherein Li is deposited on a second substrate.
[0188] Example 70. The battery of any one of examples herein, particularly example 69, wherein the second substrate is a second current collector and wherein the second current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
[0189] Example 71 . The battery of any one of examples herein, particularly examples 40-70, wherein the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of greater than 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
[0190] Example 72. The battery of any one of examples herein, particularly examples 40-71 , wherein the battery exhibits a total impedance of less than about 1500 .
[0191] Example 73. The battery of any one of examples herein, particularly examples 40-72, wherein the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg.
[0192] Example 74. The battery of any one of examples herein, particularly examples 40-73, wherein the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g when discharged at 0.1 C to 10C rate.
[0193] Example 75. The battery of any one of examples herein, particularly examples 40-74, wherein the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles.

Claims

WHAT IS CLAIMED IS:
1 . A method of forming an all-solid-state battery comprising: a) forming a cathode electrode by depositing a uniform layer of a cathode composite material, wherein the cathode composite material comprises a cathode active material and a first binder on a first substrate, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C; b) forming an electrolyte layer by depositing a uniform layer of an electrolyte material comprising at least one electrolyte on the cathode electrode and c) positioning an anode electrode on the electrolyte layer, wherein all methods steps are substantially solvent-free.
2. The method of claim 1 , further comprises a step of forming a layer of an interfacial material disposed between the electrolyte layer and the anode electrode.
3. The method of claim 1 or 2, wherein the first substrate is a first current collector.
4. The method of claim 3, wherein the first current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
5. The method of claim 3 or 4, wherein the current collector comprises aluminum, aluminum alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, stainless steel, or any combinations and alloys thereof.
6. The method of any one of claims 1 -5, wherein the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickelmanganese-cobalt oxide) cathode, NCA (nickel-cobalt-aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
7. The method of any one of claims 1 -6, wherein the first binder comprises polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
8. The method of any one of claims 1 -7, wherein the cathode active material and the binder are homogeneously pre-mixed to form the cathode composite material.
9. The method of any one of claims 1 -8, wherein the cathode composite material comprises an amount of the at least one electrolyte.
10. The method of any one of claims 1 -9, wherein the cathode composite material further comprises one or more fillers.
11 .The method of claim 10, wherein the one or more fillers comprise conductive fillers, flame retardants, flame-resistant agents, stabilizers, antibacterial agents, or any combination thereof.
12. The method of any one of claims 1 -1 1 , wherein the cathode composite material is hot pressed into the first substrate at a pressure of about 10 MPa to about
100 MPa and a temperature of about 40 °C to about 80 °C.
13. The method of any one of claims 1 -12, wherein the active cathode material is present in an amount of about 50 wt% to less than about 100 wt%.
14. The method of any one of claims 1 -13, wherein the first binder is present in an amount greater than 0 wt% to about 20 wt%.
15. The method of any one of claims 9-14, wherein the amount of the at least one electrolyte present in the cathode composite material is greater than 0 wt% to about 50 wt%.
16. The method of any one of claims 10-15, wherein the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%.
17. The method of any one of claims 1 -16, wherein the electrolyte material further comprises a second binder having a melting point equal to or less than about 70 °C.
18. The method of claim 17, wherein the second binder is the same or different as the first binder.
19. The method of claim 17 or 18, wherein the second binder is present in an amount greater than 0 wt% to about 20 wt%.
20. The method of any one of claims 1 -19, wherein the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide- based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
21 .The method of any one of claims 1 -20, wherein the at least one electrolyte comprises doped and undoped zirconium oxide (LLZO, Li?La3Zr20i2), lithium aluminum titanium phosphate (LATP, Lii.4Alo.4Tii.6(P04)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.s(P04)3), lithium zirconium chloride (LZC, Li2ZrCl6), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIC, LisInCk), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBFkLil/LiBr/LiCI), and lithium carboborates (UCB11H12), xLi2S-yP2S5, Li2S— Lil— P2S5, Li2S— Lil— U2O— P2S5, Li2S— LiBr— P2S5, U2S — U2O — P2S5, Li2S — U3PO4 — P2S5, Li2S — P2S5 — P2O5, Li2S — P2S5 — SiS2, U2S — P2S5 — SnS, Li2S — P2S5 — AI2S3, Li2S — GeS2 or Li2S — GeS2 — ZnS, LiePSsX (X=at least one of Cl, Br or I), U3PS4, U7P3S11 , LiyPSe, LiBhk, U2OHCI, LisOCIo.sBro.s, Na3SCIo.5(BCl4)o.5, or any combination thereof.
22. The method of any one of claims 17-21 , wherein the at least one electrolyte and the second binder are homogeneously pre-mixed prior to the deposition of the uniform layer.
23. The method of any one of claims 1 -22, wherein the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
24. The method of any one of claims 2-23, wherein the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li?La3Zr20i2 (LLZO), LisN, U3PS4, U3P, or a combination thereof. In some examples, the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
25. The method of claim 24, wherein the interfacial material further comprises a third binder.
26. The method of claim 25, wherein the third binder is the same or different from the first binder and/or the second binder if present.
27. The method of any one of claims 25 and 26, wherein the third binder is homogeneously pre-mixed with the active material of the interfacial material prior to forming the layer of the interfacial material.
28. The method of any one of claims 25-27, wherein the third binder is present in an amount greater than 0 wt% to about 20 wt%.
29. The method of any one of claims 2-28, the interfacial layer is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
30. The method of any one of claims 1 -29, wherein the anode electrode comprises Li metal, Li-alloys, carbon-based anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof.
31 .The method of any one of claims 1 -30, wherein the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery.
32. The method of any one of claims 1 -30, the method comprises depositing Li on a second substrate to form an anode electrode.
33. The method of claim 32, wherein the second substrate is a second current collector and wherein the second current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
34. The method of any one of claims 1 -33, wherein the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
35. The method of any one of claims 1 -34, wherein the depositing of the uniform layer of the cathode composite material and/or the uniform layer of the electrolyte material comprises doctor blade dry powder casting, melted mixing slurry coating, dry powder sprayer/coater/duster, or any combination thereof.
36. The method of any one of claims 1 -35, wherein the battery exhibits a total impedance of less than about 1500 at room temperature.
37. The method of any one of claims 1 -36, wherein the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg.
38. The method of any one of claims 1 -37, wherein the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g when discharged at 0.1 C to 10C rate.
39. The method of any one of claims 1 -38 wherein the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles.
40. A battery comprising: a) a cathode electrode comprising: i) a first substrate and ii) a cathode composite material comprising a cathode active material and a first binder, wherein the first binder is a polymeric material having a melting point equal to or less than about 70 °C and b) an electrolyte layer comprising at least one electrolyte and a second binder, wherein the second binder is a polymeric material having a melting point equal to or less than about 70 °C; wherein the second binder is the same or different from the first binder; and c) an anode electrode and wherein the battery is substantially solvent-free.
41 .The battery of claim 40, wherein the battery further comprises a layer of an interfacial material disposed between the electrolyte layer and the anode electrode.
42. The battery of claim 40 or 41 , wherein the first substrate is a first current collector.
43. The battery of claim 42, wherein the first current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
44. The battery of claim 42 or 43, wherein the current collector comprises aluminum, aluminum alloy, titanium, titanium alloy, copper, copper alloy, nickel, nickel alloy, stainless steel, or any combinations and alloys thereof.
45. The battery of any one of claims 40-44, wherein the cathode active material comprises layered oxides, vanadium-based cathode, sulfur-based cathode, manganese-based cathode, rocksalt cathode, disordered rocksalt cathode, lithium-rich cathode, high voltage ceramic, low voltage ceramic, NMC (nickelmanganese-cobalt oxide) cathode, NCA (nickel-cobalt-aluminum oxide) cathode, LCO (lithium-cobalt oxide) cathode, LFP (lithium iron phosphate) cathode, fluoride-based cathode, sulfur selenium cathode, sulfur selenium tellurium cathode, organic cathode, spinels, olivines, or any combination thereof.
46. The battery of any one of claims 40-45, wherein the first binder and/or second binder comprise polyethylene glycol, polyethylene oxide, polyvinyl butyral, polytetramethylene oxide, polyethylene adipate, polycaprolactone, low melting point agarose, poly(2-ethylene-co-(vinyl acetate)), or any combination thereof.
47. The battery of any one of claims 40-46, wherein the cathode active material and the binder are homogeneously pre-mixed to form the cathode composite material.
48. The battery of any one of claims 40-47, wherein the cathode composite material comprises an amount of the at least one electrolyte.
49. The battery of any one of claims 40-48, wherein the cathode composite material further comprises one or more fillers.
50. The battery of claim 49, wherein the one or more fillers comprise conductive fillers, flame retardants, flame-resistant agents, stabilizers, antibacterial agents, or any combination thereof.
51 .The battery of any one of claims 40-50, wherein the cathode composite material is hot pressed into the first substrate at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
52. The battery of any one of claims 40-51 , wherein the active cathode material is present in an amount of about 50 wt% to less than about 100 wt%.
53. The battery of any one of claims 40-52, wherein the first binder is present in an amount greater than 0 wt% to about 20 wt%.
54. The battery of any one of claims 40-53, wherein an amount of the at least one electrolyte present in the cathode composite material is greater than 0 wt% to about 50 wt%.
55. The battery of any one of claims 49-54, wherein the one or more fillers are present in an amount greater than 0 wt% to about 20 wt%.
56. The battery of any one of claims 40-55, wherein the second binder is present in an amount greater than 0 wt% to about 20 wt%.
57. The battery of any one of claims 40-56, wherein the at least one electrolyte comprises a sulfide-based electrolyte, an oxide-based electrolyte, a halide- based electrolyte, a hydride-based electrolyte, a nitride-based electrolyte, oxynitride-based electrolyte, garnet structure oxides, LISICON-type solids, NASICON-or KSICON-type, phosphate glass ceramics, perovskite-type and anti-perovskite type compounds, argyrodite-type, polymer-based electrolytes, or any combination thereof.
58. The battery of any one of claims 40-57, wherein the at least one electrolyte comprises doped and undoped zirconium oxide (LLZO, Li?La3Zr20i2), lithium aluminum titanium phosphate (LATP, Lii.4Alo.4Tii.6(P04)3), lithium aluminum germanium phosphate (LAGP, Lii.5Aio.5Gei.5(P04)3), lithium zirconium chloride (LZC, Li2ZrCle), lithium yttrium chloride (LYC, LisYCIe), lithium indium chloride (LIO, LisInCle), methylamine lithium borohydride (UBH4.CH3NH2), lithium borohydride-lithium halide (LiBF-kLil/LiBr/LiCI), and lithium carboborates (UCB11H12), xLi2S-yP2S5, Li2S— Lil— P2S5, Li2S— Lil— Li2O— P2S5, Li2S— LiBr— P2S5, U2S — Li2O — P2S5, Li2S — U3PO4 — P2S5, Li2S — P2S5 — P2O5, Li2S — P2S5 — SiS2, U2S — P2S5 — SnS, Li2S — P2S5 — AI2S3, Li2S — GeS2 or Li2S — GeS2 — ZnS, LiePSsX (X=at least one of Cl, Br or I), U3PS4, U7P3S11 , Li PSe, LiBH4, Li2OHCI, LisOCIosBro 5, Na3SCIo 5(BCl4)o5, or any combination thereof
59. The battery of any one of claims 40-58, wherein the at least one electrolyte and the second binder are homogeneously pre-mixed.
60. The battery of any one of claims 40-59, wherein the electrolyte layer is hot pressed with the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
61 .The battery of any one of claims 41 -60, wherein the interfacial material comprises an active material comprising LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li LaaZraO^ (LLZO), LisN, U3PS4, U3P, or a combination thereof. In some examples, the interfacial material comprises LiePSsCI (LPSCI), U7P3S11 (LPS), garnet Li7LasZr20i2 (LLZO), U3PS4, or any combination thereof.
62. The battery of claim 61 , wherein the interfacial material further comprises a third binder.
63. The battery of claim 62, wherein the third binder is the same or different from the first binder and/or second binder.
64. The battery of any one of claims 62 and 63, wherein the third binder is homogeneously pre-mixed with the active material of the interfacial material prior to forming the layer of the interfacial material.
65. The battery of any one of claims 62-64, wherein the third binder is present in an amount greater than 0 wt% to about 20 wt%.
66. The battery of any one of claims 41 -64, the interfacial layer is hot pressed with the electrolyte layer and the cathode electrode at a pressure of about 10 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
67. The battery of any one of claims 40-66, wherein the anode electrode comprises Li metal, Li-alloys, carbon-based anode and their composites, silicon anode, metal oxide anode, lithium titanate anode (LTO), titanium-niobium-based anode (TNO), organic anode, and any combination thereof.
68. The battery of any one of claims 40-67, wherein the anode electrode comprises a metal current collector serving as a substrate for an anode active material being formed in situ on a first cycling of a battery.
69. The battery of any one of claims 40-67, wherein Li is deposited on a second substrate.
70. The battery of claim 69, wherein the second substrate is a second current collector and wherein the second current collector is a film, a sheet, a foil, a mesh, a wire, or any combination thereof.
71 .The battery of any one of claims 40-70, wherein the anode electrode is hot pressed with the electrolyte layer and the cathode electrode at a pressure of greater than 0 MPa to about 100 MPa and a temperature of about 40 °C to about 80 °C.
72. The battery of any one of claims 40-71 , wherein the battery exhibits a total impedance of less than about 1500 .
73. The battery of any one of claims 40-72, wherein the battery exhibits an energy density of about 100 Wh/kg to about 500 Wh/kg.
74. The battery of any one of claims 40-73, wherein the battery exhibits a specific discharge capacity of about 50 mA h/g to about 300 mA h/g when discharged at 0.1 C to 10C rate.
75. The battery of any one of claims 40-74, wherein the battery exhibits a coulombic efficiency greater than about 70% for at least about 100 cycles.
PCT/US2024/048330 2023-10-03 2024-09-25 Materials and methods for all-solid-state batteries Pending WO2025075844A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140127579A1 (en) * 2011-06-17 2014-05-08 Zeon Corporation All-solid state secondary cell
US20180375151A1 (en) * 2015-12-31 2018-12-27 I-Ten All-solid-state battery including a solid electrolyte and a layer of ion-conducting material
US20210328206A1 (en) * 2019-05-15 2021-10-21 Lg Chem, Ltd. Electrode for All-Solid-State Battery and Method for Manufacturing Electrode Assembly Comprising the Same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140127579A1 (en) * 2011-06-17 2014-05-08 Zeon Corporation All-solid state secondary cell
US20180375151A1 (en) * 2015-12-31 2018-12-27 I-Ten All-solid-state battery including a solid electrolyte and a layer of ion-conducting material
US20210328206A1 (en) * 2019-05-15 2021-10-21 Lg Chem, Ltd. Electrode for All-Solid-State Battery and Method for Manufacturing Electrode Assembly Comprising the Same

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