Solvent-free cathode compositions and manufacturing processes

Abstract

Provided herein are solid-state cathode compositions and processes for making the solid-state cathode compositions.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of, and priority to, U.S. Provisional Patent Application No. 63 / 333,501 (filed April 21, 2022), the entire contents of which are incorporated by reference in their entirety for all purposes.

[0002] Technical Field This disclosure relates to rechargeable lithium batteries and electrodes (eg, cathodes) used in these batteries, as well as methods for preparing the batteries and electrodes. [Background technology]

[0003] background

[0003] Solid-state cathodes are advantageous for safety reasons and for energy density reasons, but they are difficult to process.

[0004]

[0004] One processing challenge is the amount of solvent used to fabricate the cathode. Another challenge is how to mix the active materials to provide the most desirable properties, such as the degree of fibrillation, in the cathode active material.

[0005]

[0005] What is needed is a process that can form a cathode with good fibrillation without using substantial amounts of solvent. Presented herein is a solution to this problem, as well as others in the field to which this disclosure pertains. Summary of the Invention [Means for solving the problem]

[0006] overview

[0006] In one embodiment, a process for manufacturing a solid-state cathode (SSC) sheet is provided herein that includes providing, or having provided, a solvent-free mixture comprising cathode active material particles, catholyte, and binder particles (wherein the binder particles are present at 1 w / w% or less); dough-kneading the mixture to form binder fibrils; and depositing the mixture to form an SSC sheet.

[0007]

[0007] In a second embodiment, a process for making a solid state cathode (SSC) sheet is presented herein that includes providing, or has provided, a solvent-free mixture including cathode active material particles, catholyte, and binder particles (wherein the binder particles are present at 5 weight percent (w / w) or less); maintaining the mixture at a temperature of about -30°C to -5°C; dough-kneading the mixture to form binder fibrils at a temperature of about 25°C to 200°C; depositing the mixture to form an SSC sheet; and thereby providing an SSC sheet. In some of these embodiments, the process includes mixing the cathode active material particles, catholyte, and binder particles prior to maintaining the mixture. In some of these embodiments, the process includes mixing the mixture while maintaining the mixture at a temperature of about -30°C to -5°C.

[0008]

[0008] In a third embodiment, a composition is provided herein comprising cathode active material particles; a binder present at 1 w / w% or less, wherein the binder is mixed with the cathode active material particles; the binder is present as fibrils; and the composition is solvent-free.

[0009] In a fourth embodiment, a composition as otherwise provided herein is prepared by a process that includes stabilizing a binder mixture and dough-kneading a cathode active material at elevated temperature. In some embodiments, the kneading is performed at a temperature between 35° C. and 200° C. In some embodiments, the kneading is performed at a temperature between 35° C. and 100° C. [Brief description of the drawings]

[0010] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1]

[0010] An embodiment of a process for manufacturing a solid-state cathode is presented. [Diagram 2]

[0011] 1 illustrates an embodiment of a manufacturing process for a solid-state cathode. [Diagram 3]

[0012] 1 is a differential scanning calorimetry (DSC) plot of the solid-state cathode. [Figure 4]

[0013] 1 is a plot of voltage (V) versus cycle active mass specific capacity (mAh / g). [Diagram 5]

[0014] 1 is a plot of area specific resistance (ASR) versus pulse index. [Figure 6]

[0015] 1 is a plot of tensile strength (stress in kPa) versus strain. [Figure 7]

[0016] 1 is a plot of sheet Young's modulus (GPa) versus sheet tensile strength (MPa) for several comparative examples. [Figure 8]

[0017] 1 is a plot of seed plastic elongation (%) versus sheet tensile strength (MPa) for several comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Detailed Description definition

[0018] As used herein, the term "about" when modifying a number, for example, about 15 w / w%, refers to a number encompassed by the modified number and, optionally, a range for that modified number, including ±10% of that number. For example, about 15 w / w% includes 15 w / w% as well as 13.5 w / w%, 14 w / w%, 14.5 w / w%, 15.5 w / w%, 16 w / w%, or 16.5 w / w%. For example, "about 75°C" includes 75°C as well as 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, or 83°C.

[0012]

[0019] As used herein, "selected from the group consisting of" refers to a single member from the group, two or more members from the group, or a combination of members from the group. Members selected from the group consisting of A, B, and C include, for example, A only, B only, or C only, as well as A and B, A and C, B and C, and A, B, and C.

[0013]

[0020] As used herein, the phrase "cathode active material" refers to a material that can reversibly insert or react with lithium ions. Examples include LiMPO4 (where M=Fe, Ni, Co, Mn); x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z O2 (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1); and LiNi x Co y Al z O2, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1. In these formulas, x, y, and z are selected such that the formulas are charge neutral.

[0014]

[0021] As used herein, the phrase "solid-state cathode" refers to a cathode that does not include any liquid phase electrolyte. As used herein, the terms "cathode" and "anode" refer to the electrodes of a battery. The cathode and anode are often referred to in the related art as positive and negative electrodes, respectively. During a charge cycle in a Li secondary battery, Li ions move away from the cathode, through the electrolyte, and to the anode. During a charge cycle, electrons move away from the cathode, through an external circuit, and to the anode. During a discharge cycle in a Li secondary battery, Li ions move through the electrolyte and from the anode toward the cathode. During a discharge cycle, electrons move away from the anode, through an external circuit, and to the cathode. As used herein, the phrase "positive electrode" refers to the electrode toward which positive ions, e.g., Li + As used herein, the phrase "negative electrode" refers to the electrode in a secondary battery through which positive ions, e.g., Li, pass, flow, or move during discharge of the battery. + Refers to an electrode in a secondary battery through which current flows or moves. A Li metal electrode and an electrode containing conversion chemistry, insertion chemistry, or combined conversion / insertion chemistry (i.e., cathode active material; e.g., NiF x , NCA, LiNi x Mn y Co z O2[NMC] or LiNi x Al y Co z In a battery containing a Li secondary battery and a NiFe2O3[NCA] (where x+y+z=1), the electrode with the conversion chemistry, insertion chemistry, or combination conversion / insertion chemistry is referred to as the positive electrode. In some applications, a cathode is used in place of the positive electrode and an anode is used in place of the negative electrode. When a Li secondary battery is charged, Li ions are transferred to the positive electrode (e.g., NiF x , NMC, NCA) to the negative electrode (e.g., Li metal). When a Li secondary battery is discharged, Li ions migrate to the positive electrode and out of the negative electrode.

[0015]

[0022] As used herein, the phrase "solid separator" refers to a Li + Ionically conductive materials (e.g., lithium) have an ionic conductivity at least 10 times higher than the electronic conductivity. 3 times, often 10 6 The term refers to a dielectric constant (DCV) that is 0.1 times larger than the positive and negative electrodes, and acts as a physical barrier or spacer between the positive and negative electrodes.

[0016]

[0023] As used herein, "LSTPS" refers to a compound of formula Li a MP b S c where M is Si, Ge, Sn, and / or Al, and where 2≦a≦8, 0.5≦b≦2.5, and 4≦c≦12. "LSPS" refers to a material characterized by the formula L a SiP b S c (wherein 2≦a≦8, 0.5≦b≦2.5, and 4≦c≦12). LSPS refers to an electrolyte material characterized by the formula L a SiP b S c where 2≦a≦8, 0.5≦b≦2.5, and 4≦c≦12. Exemplary LSTPS materials are described, for example, in International Patent Application No. PCT / US14 / 38283, SOLID STATE CATHOLYTE OR ELECTROLYTE FOR BATTERY USING LITHIUM OXIDE, filed May 15, 2014, and published on November 20, 2014 as WO 2014 / 186634, which is incorporated herein by reference. A MP B S C(M=SI, GE, AND / OR SN), which is incorporated herein by reference in its entirety. Exemplary LSTPS materials can be found, for example, in U.S. Patent Application Serial No. 14 / 618,979, filed February 10, 2015, and published June 18, 2015, as Publication No. 2015 / 0171465, which is incorporated herein by reference in its entirety. When M is Sn and Si, both are present. When M is Sn and Si, both are present. As used herein, "LSTPSO" refers to LSTPS doped with or having O present. In one embodiment, "LSTPSO" is an LSTPS material with an oxygen content of 0.01-10 atomic %. "LSPS" refers to an electrolyte material having Li, Si, P, and S chemical constituents. As used herein, "LSTPS" refers to an electrolyte material having Li, Si, P, Sn, and S chemical constituents. As used herein, "LSPSO" refers to an LSPS doped with or having O present. In one embodiment, "LSPSO" is an LSPS material with an oxygen content of 0.01-10 atomic %. As used herein, "LATP" refers to an electrolyte material having Li, As, Sn, and P chemical constituents. As used herein, "LAGP" refers to an electrolyte material having Li, As, Ge, and P chemical constituents. As used herein, "LSTPSO" refers to an electrolyte material having the formula Li a MP b S c O d where M is Si, Ge, Sn, and / or Al, where 2≦a≦8, 0.5≦b≦2.5, 4≦c≦12, and d<3. LSTPSO refers to LSTPS as defined above and with 0.1 to about 10 atomic % doping oxygen. LPSO refers to LPS as defined above and with 0.1 to about 10 atomic % doping oxygen.

[0017]

[0024] As used herein, area specific resistance (ASR) is measured by electrochemical cycling using an Arbin or Biologic instrument, unless specifically stated to the contrary.

[0018]

[0025] As used herein, ionic conductivity is measured by electrical impedance spectroscopy methods known in the art.

[0019]

[0026] As used herein, the term "electrolyte" refers to an ionically conductive and electrically insulating material. The electrolyte electrically insulates the positive and negative electrodes of a rechargeable battery while allowing the transport of ions, e.g., Li, through the electrolyte. + is useful for enabling conduction of

[0020]

[0027] As used herein, the phrase "film" or "thin film" refers to a thin membrane less than 1.0 mm thick and greater than 100 nm thick. Thin films also have a lateral dimension greater than 5 mm. A "film" or "thin film" may be produced by a continuous process such as tape-casting, slip casting, or screen printing.

[0021]

[0028] As used herein, the phrase "film thickness" refers to the distance, or center measured distance, between the top and bottom surfaces of a film. As used herein, top and bottom surfaces refer to the surfaces of the film having the largest surface area. As used herein, thickness is measured by cross-sectional scanning electron microscopy.

[0022]

[0029] As used herein, "thin" when used in reference to solid state cathode (SSC) sheets refers to a sheet or film having an average cross-sectional thickness of less than 1.0 mm and more than 20 μm. In some embodiments, the thin SSC is an SSC sheet having a thickness of 50 μm to 500 μm. In some embodiments, the thin SSC is an SSC sheet having a thickness of 10 μm to 300 μm. In some embodiments, the thin SSC is an SSC sheet having a thickness of 100 μm to 150 μm. In some embodiments, the thin SSC is an SSC sheet having a thickness of 100 μm to 120 μm. In some embodiments, the thin SSC is an SSC sheet having a thickness of 80 μm to 100 μm.

[0023]

[0030] As used herein, "binder" refers to a polymer that has the ability to increase the adhesive and cohesive strength of a material, such as the solids content in a green tape. Suitable binders include, but are not limited to, PVDF, PVDF-HFP, SBR, and ethylene alpha-olefin copolymers. "Binder" refers to a material that aids in adhering another material. For example, as used herein, polyvinyl butyral is a binder because it is useful for adhering garnet materials. Other binders may include polycarbonates. Other binders may include polyacrylates and polymethacrylates. These examples of binders are not limiting with respect to the overall scope of binders contemplated herein, but serve only as examples. Binders useful in the present disclosure include, but are not limited to, polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefins, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylic resins), acrylics, polyvinylacetacetal resin, polyvinylbutyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, silicones, and the like.In some examples, including any of the foregoing, the binder may be polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl The polymer is selected from the group consisting of poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene fluoride (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA).

[0024]

[0031] As used herein, the term "electrolyte" refers to an ionically conductive and electrically insulating material. The electrolyte electrically insulates the positive and negative electrodes of a rechargeable battery while allowing the flow of ions, e.g., Li, through the electrodes. + In some of the electrochemical devices described herein, the electrolyte includes a Li-ion-doped garnet, such as a lithium-loaded garnet. + The electrolyte may be a solid-state film, pellet, or monolith of a conductive oxide. In some examples, the electrolyte may be a gel electrolyte that is laminated to or in direct contact with the solid film, pellet, or monolith.

[0025]

[0032] As used herein, "solid state thin film or pellet separator" refers to a solid state electrolyte that may exist as a thin film or a pressed powder pellet. The thin film or pellet may be a sintered or unsintered Li-ion battery, such as lithium-loaded garnet. + It may include a conductive oxide.

[0026]

[0033] As used herein, the term "solid state electrolyte" refers to an electrolyte, as defined herein, in which the electrolyte is a solid.

[0027]

[0034] As used herein, the terms "separator" and "Li+ ion conducting separator" are used interchangeably with separator, which is a shorthand reference to Li+ ion conducting separator, unless expressly stated otherwise. Separator refers to a solid-state electrolyte that conducts Li+ ions, substantially insulates electrons, and is suitable for use as a physical barrier or spacer between positive and negative electrodes in an electrochemical cell or rechargeable battery. As used herein, a separator is substantially insulating to electrons. The lithium ion conductivity of the separator is at least 103 times, typically 106 times, greater than the electronic conductivity of the separator.

[0028]

[0035] As used herein, the phrase "lithium filled garnet" refers to an oxide characterized by a crystal structure related to the garnet crystal structure. Lithium filled garnets include those oxides of the formula Li A La B Zr C O F , Li A La B M' C M” D Ta E O F , or Li A La B M' C M” D Nb E O F(where 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2; 0 < E < 2.5, 10 < F < 13, and M’ and M” are each independently selected from Al, Mo, W, Nb, Ga, Sb, Ca, Ba, Sr, Ce, Hf, Rb, and Ta in each case); or Li a La b Zr c Al d Me” e O f (where 5 < a < 7.7; 2 < b < 4; 0 < c ≤ 2.5; 0 < d < 2; 0 < e < 2, 10 < f < 13, and Me” is a metal selected from Nb, V, W, Mo, Ta, Ga, and Sb). Garnets as used herein also include those garnets doped with Al or Al2O3. Also, garnets as used herein include Li A La B Zr C O F + yAl2O3 (where x can be 5.8 - 7.0 and y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0, and where 4 < A < 8.5, 1.5 < B < 4, 0 < C ≤ 2, 0 < D < 2; 10 < F < 13), but are not limited thereto. Also, garnets as used herein include Li x La3Zr2O 12 + yAl2O3 (where x can be 5.8 - 7.0 and y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0), but are not limited thereto. When used herein, garnet is YAG - garnet (i.e., yttrium aluminum garnet, e.g., Y3Al5O 12As used herein, garnet does not include silicate-based garnets such as pyrope, almandine, spessartine, grossular, hessonite, or yellow garnet, tsarborite, uvarovite, and andradite, and the solid solutions pyrope-almandine-spessarite and uvarovite-grossular-andradite. Garnet in this specification does not include nesosilicates having the general formula X3Y2(SiO4)3, where X is Ca, Mg, Fe, and / or Mn; Y is Al, Fe, and / or Cr.

[0029]

[0036] As used herein, the phrases "garnet precursor chemicals" or "chemical precursors of a garnet-type electrolyte" refer to chemicals that react to form the lithium-filled garnet materials described herein. These chemical precursors include, but are not limited to, lithium hydroxide (e.g., LiOH), lithium oxide (e.g., Li2O), lithium carbonate (e.g., Li2CO3), zirconium oxide (e.g., ZrO2), lanthanum oxide (e.g., La2O3), aluminum oxide (e.g., Al2O3), aluminum (e.g., Al), aluminum nitrate (e.g., AlNO3), aluminum nitrate monohydrate, niobium oxide (e.g., Nb2O5), and tantalum oxide (e.g., Ta2O5).

[0030]

[0037] As used herein, the term "d 50 "Diameter" refers to the median diameter in a distribution of sizes as measured by microscopy or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 50 includes the characteristic dimension below which 50% of the particles are smaller than the recited size.

[0031]

[0038] As used herein, the term "d 90"Diameter" refers to a size in a distribution of sizes as measured by microscopy techniques or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. 90 includes the characteristic dimension below which 90% of the particles are smaller than the listed size.

[0032]

[0039] As used herein, the term "catholyte" refers to a liquid or gel electrolyte confined within the positive electrode space of an electrochemical cell. Catholyte also refers to a Li-ion conductor that is intimately mixed with, or surrounds and is in contact with, the positive electrode active material, and provides an ionic pathway for Li+ to and from the active material. Catholyte may also be a liquid, gel, semi-liquid, semi-solid, polymer, and / or solid polymer ionic conductor. In some examples, catholyte includes the gels described herein. In some examples, gel electrolytes include any electrolytes described herein, such as nitriles, dinitriles, organic sulfur-containing solvents, or combinations thereof described herein.

[0033] composition

[0040] Presented herein are compositions including: cathode active material particles; and binder particles present at 1 w / w% or less (e.g., 1, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, or 0.1%), where the binder is mixed with the cathode active material particles; the binder is present as fibrils; and the composition is solvent-free.

[0034]

[0041] In some embodiments, including any of the foregoing, the binder is present at 0.3% w / w or less (e.g., 0.25, 0.20, 0.15, 0.10, 0.075, or 0.05%).

[0035]

[0042] In some embodiments, including any of the foregoing, the binder is poly(tetrafluoroethylene) (PTFE).

[0036]

[0043] In some embodiments, including any of the foregoing, the binder is PTFE or poly(vinylpyrrolidone) (PVP).

[0037]

[0044] In some embodiments, including any of the above, the PTFE binder particle size is <2mm. In some embodiments, including any of the above, the PTFE binder particle size is <1.5mm. In some embodiments, including any of the above, the PTFE binder particle size is <1mm. In some embodiments, including any of the above, the PTFE binder particle size is <0.75mm. In some embodiments, including any of the above, the PTFE binder particle size is <0.5mm.

[0038]

[0045] In some embodiments, including any of the foregoing, the binder is PTFE and at least one additional binder.

[0039]

[0046] In some embodiments, including any of the foregoing, the binder may be PTFE, as well as polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene rubber (SBR), polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefin, polyethylene. Polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (PMMA) (and other acrylic resins), acrylic, polyvinyl acetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide and at least one additional binder selected from poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), and combinations thereof.

[0040]

[0047] In some embodiments, including any of the foregoing, the cathode active material is a material set forth in International Patent Application Publication No. PCT / US2021 / 049528, filed September 8, 2021, and entitled CATHODE COATING, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0041]

[0048] In some embodiments, including any of the foregoing, the cathode active material is LiMPO4 (wherein M=Fe, Ni, Co, Mn); x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z O2 (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1); and LiNi x Co y Al z O2 (wherein x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1).

[0042]

[0049] In some embodiments, including any of the foregoing, the cathode active material is LiNi x Mn y Co z O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0043]

[0050] In some embodiments, including any of the foregoing, the cathode active material is LiNi x Mn y Co z O2(x is 0.8, y is 0.1, and z is 0.1).

[0044]

[0051] In some embodiments, including any of the foregoing, the cathode active material is LiNi x Mn y Co z O2(x is 0.6, y is 0.2, and z is 0.2).

[0045]

[0052] In some embodiments, including any of the foregoing, the cathode active material is LiNi x Mn y Co z O2 (x is 0.5, y is 0.3, and z is 0.2).

[0046]

[0053] In some embodiments, including any of the foregoing, the cathode active material is LiNi x Mn y Co z O2(x is 1 / 3, y is 1 / 3, z is 1 / 3).

[0047]

[0054] In some embodiments, including any of the foregoing, the cathode active material is Li(NiCoMn)O 2 .

[0048]

[0055] In some embodiments, including any of the foregoing, the cathode active material is LiFePO4.

[0049]

[0056] In some embodiments, including any of the foregoing, the NMC is 0.1 μm <S<50μmの、d 50 The particle size is S.

[0050]

[0057] In some embodiments, including any of the foregoing, the NMC is 0.5 μm <S<30μmの、d 50 The particle size is S.

[0051]

[0058] In some embodiments, including any of the foregoing, the NMC is 1 μm <S<20μmの、d 50 The particle size is S.

[0052]

[0059] In some embodiments, including any of the foregoing, the NMC is 2 μm <S<15μmの、d 50 The particle size is S.

[0053]

[0060] In some embodiments, including any of the foregoing, the NMC is 3 μm <S<12μmの、d 50 The particle size is S.

[0054]

[0061] In some embodiments, including any of the foregoing, the NMC is 4 μm <S<10μmの、d 50 The particle size is S.

[0055]

[0062] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.005 μm or less. <T<20μmの、d 50 The particle size is T.

[0056]

[0063] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.01 μm or less. <T<10μmの、d 50 The particle size is T.

[0057]

[0064] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.02 μm or less. <T<10μmの、d 50 The particle size is T.

[0058]

[0065] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.05 μm or less. <T<8μmの、d 50 The particle size is T.

[0059]

[0066] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.02 μm or less. <T<5μmの、d 50 The particle size is T.

[0060]

[0067] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.05 μm or less. <T<3μmの、d 50 The particle size is T.

[0061]

[0068] In some embodiments, including any of the foregoing, the catholyte has a particle size of 0.1 μm or less. <T<1.5μmの、d 50 The particle size is T.

[0062]

[0069] In some embodiments, including any of the above, the composition comprises 2 to 2.5 g / cm 3 (e.g., about 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, or 2.6).

[0063]

[0070] Presented herein are thin sheets comprising the compositions provided herein in some embodiments, including any of the foregoing.

[0064]

[0071] In some embodiments, including any of the foregoing, the catholyte is a LSTPS.

[0065]

[0072] In some embodiments, including any of the foregoing, the catholyte is arginine.

[0066]

[0073] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting sulfide, for example, Li2S-SiS2.

[0067]

[0074] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting oxide, for example a lithium loaded garnet.

[0068]

[0075] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting halide, such as perovskite.

[0069]

[0076] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting organic polymer, for example, LiPF6 in PEO.

[0070]

[0077] In some embodiments, including any of the foregoing, the cathode active loading in the cathode is between 1 and 15 mAh / cm 2 It is.

[0071]

[0078] In some embodiments, including any of the foregoing, the cathodic active loading is at least 5 mAh / cm 2 Between.

[0072]

[0079] In some embodiments, including any of the foregoing, the sheet has a thickness of 120 μm.

[0073]

[0080] In some embodiments, including any of the foregoing, the sheet has a thickness of 150 μm.

[0074]

[0081] In some embodiments, including any of the foregoing, the sheet is at least 5 centimeters (cm) wide.

[0075]

[0082] In some embodiments, including any of the foregoing, the sheet is at least 1 meter (m) wide.

[0076]

[0083] In some embodiments, including any of the foregoing, the sheet is at least 10 cm in length.

[0077]

[0084] In some embodiments, including any of the foregoing, the sheet is at least 70 cm in length.

[0078]

[0085] In some embodiments, including any of the foregoing, the sheet is 100 mm by 2,000 mm.

[0079]

[0086] In some embodiments, including any of the foregoing, the sheet is 150 mm by 100 m.

[0080]

[0087] In some embodiments, including any of the foregoing, the sheet is a 300 mm by continuous roll.

[0081]

[0088] In some embodiments, including any of the foregoing, the sheet is at least 1 m in length.

[0082]

[0089] In some embodiments, including any of the foregoing, a bilayer is provided herein that includes a metal layer in contact with two thin sheets provided herein.

[0083]

[0090] In some embodiments, including any of the foregoing, a trilayer is provided herein that includes a metal layer between and in contact with two of the thin sheets provided herein.

[0084]

[0091] In some embodiments, including any of the foregoing, the metal layer is a layer of Al.

[0085]

[0092] In some embodiments, including any of the foregoing, the metal layer is a layer of Ni.

[0086]

[0093] In some embodiments, including any of the above, the electrode prior to death has a porosity range of 40% to 50% (eg, about 35, 40, 45, 50, or 55% porosity).

[0087]

[0094] In some embodiments, including any of the foregoing, the electrode product has a tensile strength of about 0.3 to 0.5 MPa (eg, 0.28, 0.3, 0.33, 0.35, 0.38, 0.4, 0.43, 0.45, 0.48, or 0.5 MPa).

[0088]

[0095] In some embodiments, including any of the foregoing, the electrode product has a Young's modulus of about 0.5 to 0.8 MPa (e.g., 0.48, 0.5, 0.53, 0.55, 0.58, 0.6, 0.63, 0.65, 0.68, 0.7, 0.73, 0.75, 0.78, or 0.8 MPa).

[0089]

[0096] In some embodiments, including any of the foregoing, the electrode product has a plastic elongation of about 5-15% (e.g., about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15%).

[0090]

[0097] In some embodiments, including any of the foregoing, the electrode product has an elasticity of about 0.01 to 0.15 GPa (e.g., about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, or 0.15 GPa).

[0091]

[0098] In some embodiments, compositions as otherwise described herein are prepared by a process that includes dough-kneading the cathode active material at low temperature (ie, "cold kneading").

[0092]

[0099] In some embodiments, compositions as otherwise described herein are prepared by a process that includes stabilizing the binder at a low temperature and dough-kneading the cathode active material at a higher temperature, in some embodiments, such kneading is performed at a temperature between 25° C. and 200° C. (e.g., 45° C.).

[0093] process [000100] Presented herein is a process for making a solid state cathode (SSC) sheet, the process comprising providing, or having provided, a solvent-free mixture comprising cathode active material particles, catholyte, and binder particles, wherein the binder particles are present at 1 w / w% or less (e.g., 1, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, or 0.1%); dough kneading the mixture to form binder fibrils; and depositing the mixture to form a SSC sheet.

[0094] [000101] In some embodiments, including any of the foregoing, provided herein is a process for making a solid-state cathode (SSC) sheet, the process including providing, or having provided, a solvent-free mixture including cathode active material particles, catholyte, and binder particles (wherein the binder particles are present at 5 w / w% or less); maintaining the mixture at a temperature of about -30°C to -5°C; dough-kneading the mixture to form binder fibrils at a temperature of about 25°C to 200°C; and depositing the mixture to form an SSC sheet.

[0095] [000102] In some embodiments, including any of the foregoing, dough-kneading the mixture to form binder fibrils includes shearing the cathode active material particles and the binder particles to form the binder fibrils.

[0096] [000103] In some embodiments, including any of the foregoing, dough-kneading the mixture to form binder fibrils further includes compressing the cathode active material particles and the binder particles to create a network of binder fibrils throughout the cathode active material particles.

[0097] [000104] In some embodiments, including any of the above, the process includes pressing the cathode using a roller and forming and networking PTFE fibrils in the cathode. In some embodiments, the process includes applying a calendar press in the final stage of the process to densify the cathode.

[0098] [000105] In some embodiments, including any of the foregoing, kneading the mixture into a dough comprises using a mortar.

[0099] [000106] In some embodiments, including any of the above, the dough mixing of the mixture includes the use of a twin screw co-rotating extruder. Commercial embodiments of such extruders include, but are not limited to, Process 11 by Themo Fisher; or 20MM Twin Screw Mixing Line by Buhler. Other manufacturers include Coperion.

[0100] [000107] In some embodiments, including any of the foregoing, the process further includes pre-treating the binder. For example, pre-treating can include, but is not limited to, atomization of the PTFE powder. One method of atomizing the PTFE powder is blade mixing at a low temperature. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 10°C. In some embodiments, the low temperature is below the phase transition temperature. In some embodiments, the low temperature is at the phase transition temperature. In certain embodiments, the low temperature is 11°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 12°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 13°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 14°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 15°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 16°C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 17° C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 18° C. In certain embodiments, the low temperature is 19° C. In some embodiments, the low temperature is below the phase transition temperature. In certain embodiments, the low temperature is 20° C.

[0101] [000108] In some embodiments, including any of the foregoing, the process further includes stabilizing the binder. For example, stabilization includes, but is not limited to, maintaining the mixture, e.g., at a low temperature; and further mixing the binder (e.g., PTFE) powder, e.g., by blade mixing at the low temperature. In some embodiments, the low temperature is below the phase transition temperature. In some embodiments, the low temperature is below the phase transition temperature. In some embodiments, the low temperature is at the phase transition temperature. In certain embodiments, the low temperature is about -40°C to 0°C. In certain embodiments, the low temperature is about -30°C to -5°C. In certain embodiments, the low temperature is -30°C. In certain embodiments, the low temperature is -29°C. In certain embodiments, the low temperature is -28°C. In certain embodiments, the low temperature is -27°C. In certain embodiments, the low temperature is -26°C. In certain embodiments, the low temperature is -25°C. In certain embodiments, the low temperature is -24°C. In certain embodiments, the low temperature is -23°C. In certain embodiments, the low temperature is -22°C. In certain embodiments, the low temperature is -21°C. In certain embodiments, the low temperature is -20°C. In certain embodiments, the low temperature is -19°C. In certain embodiments, the low temperature is -18°C. In certain embodiments, the low temperature is -17°C. In certain embodiments, the low temperature is -16°C. In certain embodiments, the low temperature is -15°C. In certain embodiments, the low temperature is -14°C. In certain embodiments, the low temperature is -13°C. In certain embodiments, the low temperature is -12°C. In certain embodiments, the low temperature is -11°C. In certain embodiments, the low temperature is -10°C. In certain embodiments, the low temperature is -9°C. In certain embodiments, the low temperature is -8°C. In certain embodiments, the low temperature is -7°C. In certain embodiments, the low temperature is -6°C. In certain embodiments, the low temperature is -5°C. In certain embodiments, the low temperature is -4°C. In certain embodiments, the low temperature is -3°C. In certain embodiments, the low temperature is -2°C. In certain embodiments, the low temperature is −1° C. In certain embodiments, the low temperature is 0° C.

[0102] [000109] In some embodiments, the stabilization of the binder comprises maintaining the mixture at a low temperature for at least 1 hour. In some embodiments, the stabilization of the binder comprises such maintaining for at least 1.5 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 2 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 2.5 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 3 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 3.5 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 4 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 5 hours. In some embodiments, the stabilization of the binder comprises such maintaining for at least 6 hours.

[0103] [000110] In some embodiments, stabilizing the binder includes further mixing (e.g., by blade mixing). In some embodiments, mixing is for at least 10x for at least 1 hour (e.g., 10x 2 seconds at 20,000 rpm). In some embodiments, the composition is cooled during mixing (e.g., in a cryogenic environment). In some embodiments, the composition is cooled between mixing (e.g., in a cryogenic environment).

[0104] [000111] In some embodiments, including any of the above, dough kneading occurs at a temperature of about 18°C ​​to about 180°C. In some embodiments, dough kneading occurs at a temperature of about 50°C to about 80°C. In some embodiments, dough kneading occurs at a temperature of about 60°C to about 80°C. In some embodiments, dough kneading occurs at a temperature of about 70°C to about 80°C. In some embodiments, dough kneading occurs at a temperature of about 80°C to about 100°C. In some embodiments, dough kneading occurs at a temperature of about 90°C to about 100°C. In some embodiments, dough kneading occurs at a temperature of about 18°C. In some embodiments, dough kneading occurs at a temperature of about 19°C. In some embodiments, dough kneading occurs at a temperature of about 20°C. In some embodiments, dough kneading occurs at a temperature of about 21°C. In some embodiments, dough kneading occurs at a temperature of about 22°C. In some embodiments, dough kneading occurs at a temperature of about 23°C. In some embodiments, dough kneading occurs at a temperature of about 24°C. In some embodiments, dough kneading occurs at a temperature of about 25° C. In some embodiments, dough kneading occurs at a temperature of about 26° C. In some embodiments, dough kneading occurs at a temperature of about 27° C. In some embodiments, dough kneading occurs at a temperature of about 28° C. In some embodiments, dough kneading occurs at a temperature of about 29° C. In some embodiments, dough kneading occurs at a temperature of about 30° C. In some embodiments, dough kneading occurs at a temperature of about 31° C. In some embodiments, dough kneading occurs at a temperature of about 32° C. In some embodiments, dough kneading occurs at a temperature of about 33° C. In some embodiments, dough kneading occurs at a temperature of about 34° C. In some embodiments, dough kneading occurs at a temperature of about 35° C. In some embodiments, dough kneading occurs at a temperature of about 36° C. In some embodiments, dough kneading occurs at a temperature of about 37° C. In some embodiments, dough kneading occurs at a temperature of about 38° C. In some embodiments, dough kneading occurs at a temperature of about 39° C. In some embodiments, dough kneading occurs at a temperature of about 40° C. In some embodiments, dough mixing occurs at a temperature of about 41°C.In some embodiments, dough kneading occurs at a temperature of about 42° C. In some embodiments, dough kneading occurs at a temperature of about 43° C. In some embodiments, dough kneading occurs at a temperature of about 44° C. In some embodiments, dough kneading occurs at a temperature of about 45° C. In some embodiments, dough kneading occurs at a temperature of about 46° C. In some embodiments, dough kneading occurs at a temperature of about 47° C. In some embodiments, dough kneading occurs at a temperature of about 48° C. In some embodiments, dough kneading occurs at a temperature of about 49° C. In some embodiments, dough kneading occurs at a temperature of about 50° C. In some embodiments, dough kneading occurs at a temperature of about 51° C. In some embodiments, dough kneading occurs at a temperature of about 52° C. In some embodiments, dough kneading occurs at a temperature of about 53° C. In some embodiments, dough kneading occurs at a temperature of about 54° C. In some embodiments, dough kneading occurs at a temperature of about 55° C. In some embodiments, dough kneading occurs at a temperature of about 56° C. In some embodiments, dough kneading occurs at a temperature of about 57° C. In some embodiments, dough kneading occurs at a temperature of about 58° C. In some embodiments, dough kneading occurs at a temperature of about 59° C. In some embodiments, dough kneading occurs at a temperature of about 60° C. In some embodiments, dough kneading occurs at a temperature of about 61° C. In some embodiments, dough kneading occurs at a temperature of about 62° C. In some embodiments, dough kneading occurs at a temperature of about 63° C. In some embodiments, dough kneading occurs at a temperature of about 64° C. In some embodiments, dough kneading occurs at a temperature of about 65° C. In some embodiments, dough kneading occurs at a temperature of about 66° C. In some embodiments, dough kneading occurs at a temperature of about 67° C. In some embodiments, dough kneading occurs at a temperature of about 68° C. In some embodiments, dough kneading occurs at a temperature of about 69° C. In some embodiments, dough kneading occurs at a temperature of about 70° C. In some embodiments, dough kneading occurs at a temperature of about 71° C. In some embodiments, dough kneading occurs at a temperature of about 72° C. In some embodiments, dough kneading occurs at a temperature of about 73° C.In some embodiments, dough kneading occurs at a temperature of about 74°C. In some embodiments, dough kneading occurs at a temperature of about 75°C. In some embodiments, dough kneading occurs at a temperature of about 76°C. In some embodiments, dough kneading occurs at a temperature of about 77°C. In some embodiments, dough kneading occurs at a temperature of about 78°C. In some embodiments, dough kneading occurs at a temperature of about 79°C. In some embodiments, dough kneading occurs at a temperature of about 80°C. In some embodiments, dough kneading occurs at a temperature of about 81°C. In some embodiments, dough kneading occurs at a temperature of about 82°C. In some embodiments, dough kneading occurs at a temperature of about 83°C. In some embodiments, dough kneading occurs at a temperature of about 84°C. In some embodiments, dough kneading occurs at a temperature of about 85°C. In some embodiments, dough kneading occurs at a temperature of about 86°C. In some embodiments, dough kneading occurs at a temperature of about 87°C. In some embodiments, dough kneading occurs at a temperature of about 88°C. In some embodiments, dough kneading occurs at a temperature of about 89°C. In some embodiments, dough kneading occurs at a temperature of about 90° C. In some embodiments, dough kneading occurs at a temperature of about 91° C. In some embodiments, dough kneading occurs at a temperature of about 92° C. In some embodiments, dough kneading occurs at a temperature of about 93° C. In some embodiments, dough kneading occurs at a temperature of about 94° C. In some embodiments, dough kneading occurs at a temperature of about 95° C. In some embodiments, dough kneading occurs at a temperature of about 96° C. In some embodiments, dough kneading occurs at a temperature of about 97° C. In some embodiments, dough kneading occurs at a temperature of about 98° C. In some embodiments, dough kneading occurs at a temperature of about 99° C. In some embodiments, dough kneading occurs at a temperature of about 100° C. In some embodiments, dough kneading occurs at a temperature of about 101° C. In some embodiments, dough kneading occurs at a temperature of about 102° C. In some embodiments, dough kneading occurs at a temperature of about 103° C. In some embodiments, dough kneading occurs at a temperature of about 104° C.In some embodiments, dough kneading occurs at a temperature of about 105°C. In some embodiments, dough kneading occurs at a temperature of about 106°C. In some embodiments, dough kneading occurs at a temperature of about 107°C. In some embodiments, dough kneading occurs at a temperature of about 108°C. In some embodiments, dough kneading occurs at a temperature of about 109°C. In some embodiments, dough kneading occurs at a temperature of about 110°C. In some embodiments, dough kneading occurs at a temperature of about 111°C. In some embodiments, dough kneading occurs at a temperature of about 112°C. In some embodiments, dough kneading occurs at a temperature of about 113°C. In some embodiments, dough kneading occurs at a temperature of about 114°C. In some embodiments, dough kneading occurs at a temperature of about 115°C. In some embodiments, dough kneading occurs at a temperature of about 116°C. In some embodiments, dough kneading occurs at a temperature of about 117°C. In some embodiments, dough kneading occurs at a temperature of about 118°C.

[0105] [000112] In some embodiments, dough kneading occurs at a temperature of about 119°C. In some embodiments, dough kneading occurs at a temperature of about 120°C. In some embodiments, dough kneading occurs at a temperature of about 121°C. In some embodiments, dough kneading occurs at a temperature of about 122°C. In some embodiments, dough kneading occurs at a temperature of about 123°C. In some embodiments, dough kneading occurs at a temperature of about 124°C. In some embodiments, dough kneading occurs at a temperature of about 125°C. In some embodiments, dough kneading occurs at a temperature of about 126°C. In some embodiments, dough kneading occurs at a temperature of about 127°C. In some embodiments, dough kneading occurs at a temperature of about 128°C. In some embodiments, dough kneading occurs at a temperature of about 129°C. In some embodiments, dough kneading occurs at a temperature of about 130°C. In some embodiments, dough kneading occurs at a temperature of about 131°C. In some embodiments, dough kneading occurs at a temperature of about 132°C. In some embodiments, dough kneading occurs at a temperature of about 133° C. In some embodiments, dough kneading occurs at a temperature of about 134° C. In some embodiments, dough kneading occurs at a temperature of about 135° C. In some embodiments, dough kneading occurs at a temperature of about 136° C. In some embodiments, dough kneading occurs at a temperature of about 137° C. In some embodiments, dough kneading occurs at a temperature of about 138° C. In some embodiments, dough kneading occurs at a temperature of about 139° C. In some embodiments, dough kneading occurs at a temperature of about 140° C. In some embodiments, dough kneading occurs at a temperature of about 141° C. In some embodiments, dough kneading occurs at a temperature of about 142° C. In some embodiments, dough kneading occurs at a temperature of about 143° C. In some embodiments, dough kneading occurs at a temperature of about 144° C. In some embodiments, dough kneading occurs at a temperature of about 145° C. In some embodiments, dough kneading occurs at a temperature of about 146° C. In some embodiments, dough mixing occurs at a temperature of about 147° C. In some embodiments, dough mixing occurs at a temperature of about 148° C.In some embodiments, dough kneading occurs at a temperature of about 149°C. In some embodiments, dough kneading occurs at a temperature of about 150°C. In some embodiments, dough kneading occurs at a temperature of about 151°C. In some embodiments, dough kneading occurs at a temperature of about 152°C. In some embodiments, dough kneading occurs at a temperature of about 153°C. In some embodiments, dough kneading occurs at a temperature of about 154°C. In some embodiments, dough kneading occurs at a temperature of about 155°C. In some embodiments, dough kneading occurs at a temperature of about 156°C. In some embodiments, dough kneading occurs at a temperature of about 157°C. In some embodiments, dough kneading occurs at a temperature of about 158°C. In some embodiments, dough kneading occurs at a temperature of about 159°C. In some embodiments, dough kneading occurs at a temperature of about 160°C. In some embodiments, dough kneading occurs at a temperature of about 161°C. In some embodiments, dough kneading occurs at a temperature of about 162°C. In some embodiments, dough kneading occurs at a temperature of about 163°C. In some embodiments, dough kneading occurs at a temperature of about 164°C. In some embodiments, dough kneading occurs at a temperature of about 165°C. In some embodiments, dough kneading occurs at a temperature of about 166°C. In some embodiments, dough kneading occurs at a temperature of about 167°C. In some embodiments, dough kneading occurs at a temperature of about 168°C. In some embodiments, dough kneading occurs at a temperature of about 169°C. In some embodiments, dough kneading occurs at a temperature of about 170°C. In some embodiments, dough kneading occurs at a temperature of about 171°C. In some embodiments, dough kneading occurs at a temperature of about 172°C. In some embodiments, dough kneading occurs at a temperature of about 173°C. In some embodiments, dough kneading occurs at a temperature of about 174°C. In some embodiments, dough kneading occurs at a temperature of about 175°C. In some embodiments, dough kneading occurs at a temperature of about 176°C. In some embodiments, dough mixing occurs at a temperature of about 177° C. In some embodiments, dough mixing occurs at a temperature of about 178° C.In some embodiments, dough kneading occurs at a temperature of about 179°C. In some embodiments, dough kneading occurs at a temperature of about 180°C. In some embodiments, dough kneading occurs at a temperature of about 181°C. In some embodiments, dough kneading occurs at a temperature of about 182°C. In some embodiments, dough kneading occurs at a temperature of about 183°C. In some embodiments, dough kneading occurs at a temperature of about 184°C. In some embodiments, dough kneading occurs at a temperature of about 185°C. In some embodiments, dough kneading occurs at a temperature of about 186°C. In some embodiments, dough kneading occurs at a temperature of about 187°C. In some embodiments, dough kneading occurs at a temperature of about 188°C. In some embodiments, dough kneading occurs at a temperature of about 189°C. In some embodiments, dough kneading occurs at a temperature of about 190°C. In some embodiments, dough kneading occurs at a temperature of about 191°C. In some embodiments, dough kneading occurs at a temperature of about 192°C. In some embodiments, dough kneading occurs at a temperature of about 193° C. In some embodiments, dough kneading occurs at a temperature of about 194° C. In some embodiments, dough kneading occurs at a temperature of about 195° C. In some embodiments, dough kneading occurs at a temperature of about 196° C. In some embodiments, dough kneading occurs at a temperature of about 197° C. In some embodiments, dough kneading occurs at a temperature of about 198° C. In some embodiments, dough kneading occurs at a temperature of about 199° C. In some embodiments, dough kneading occurs at a temperature of about 200° C.

[0106] [000113] In some embodiments, including any of the above, dough kneading occurs at a temperature of from about 21°C to about 31°C.

[0107] [000114] In some embodiments, including any of the above, dough mixing occurs at a temperature of from about 21°C to about 65°C.

[0108] [000115] In some embodiments, including any of the above, dough mixing occurs at a temperature of from about 31°C to about 65°C.

[0109] [000116] In some embodiments, including any of the above, dough kneading occurs at a temperature of from about 31°C to about 85°C.

[0110] [000117] In some embodiments, including any of the foregoing, dough kneading occurs at a temperature of about 75°C.

[0111] [000118] In some embodiments, including any of the above, dough kneading occurs at a temperature of about 25°C to about 200°C. In some embodiments, including any of the above, dough kneading occurs at a temperature of about 30°C to about 60°C. In some embodiments, including any of the above, dough kneading occurs at a temperature of about 40°C to about 80°C. In some embodiments, including any of the above, dough kneading occurs at a temperature of about 50°C to about 100°C. In some embodiments, dough kneading occurs at a temperature of about 60°C to about 120°C. In some embodiments, dough kneading occurs at a temperature of about 70°C to about 140°C. In some embodiments, dough kneading occurs at a temperature of about 80°C to about 160°C. In some embodiments, dough kneading occurs at a temperature of about 90°C to about 180°C. In some embodiments, including any of the above, dough kneading occurs at a temperature of about 45°C. In some embodiments, dough kneading occurs at a temperature of about 50°C. In some embodiments, dough kneading occurs at a temperature of about 55° C. In some embodiments, dough kneading occurs at a temperature of about 60° C. In some embodiments, dough kneading occurs at a temperature of about 65° C. In some embodiments, dough kneading occurs at a temperature of about 70° C. In some embodiments, dough kneading occurs at a temperature of about 75° C. In some embodiments, dough kneading occurs at a temperature of about 80° C. In some embodiments, dough kneading occurs at a temperature of about 85° C. In some embodiments, dough kneading occurs at a temperature of about 90° C. In some embodiments, dough kneading occurs at a temperature of about 95° C. In some embodiments, dough kneading occurs at a temperature of 100° C. In some embodiments, dough kneading occurs at a temperature of about 105° C. In some embodiments, dough kneading occurs at a temperature of about 110° C. In some embodiments, dough kneading occurs at a temperature of about 115° C. In some embodiments, dough kneading occurs at a temperature of about 120° C. In some embodiments, dough kneading occurs at a temperature of about 125° C. In some embodiments, dough mixing occurs at a temperature of about 130° C. In some embodiments, dough mixing occurs at a temperature of about 135° C. In some embodiments, dough mixing occurs at a temperature of 140° C.In some embodiments, dough kneading occurs at a temperature of about 145°C. In some embodiments, dough kneading occurs at a temperature of about 150°C. In some embodiments, dough kneading occurs at a temperature of about 155°C. In some embodiments, dough kneading occurs at a temperature of about 160°C. In some embodiments, dough kneading occurs at a temperature of about 165°C. In some embodiments, dough kneading occurs at a temperature of about 170°C. In some embodiments, dough kneading occurs at a temperature of about 175°C. In some embodiments, dough kneading occurs at a temperature of about 180°C. In some embodiments, dough kneading occurs at a temperature of about 185°C. In some embodiments, dough kneading occurs at a temperature of about 190°C. In some embodiments, dough kneading occurs at a temperature of about 195°C. In some embodiments, dough kneading occurs at a temperature of about 200°C.

[0112] [000119] In some embodiments, including any of the foregoing, dough kneading occurs at a temperature of about 45°C.

[0113] [000120] In some embodiments, the method further includes densifying the electrode by any method used by one of ordinary skill in the art. In some embodiments, densification is by applying high pressure in a uniaxial press. In some embodiments, densification is by applying high pressure in an isostatic press. In some embodiments, densification is by calendering the electrode.

[0114] [000121] In some embodiments, the pressure applied during densification is between about 400 MPa and 1 GPa (e.g., 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000 MPa).

[0115] [000122] In some embodiments, including any of the above, the binder particles are present at 0.3 w / w% or less.

[0116] [000123] In some embodiments, including any of the above, the binder is PTFE.

[0117] [000124] In some embodiments, including any of the above, the binder is PTFE and at least one additional binder.

[0118] [000125] In some embodiments, including any of the foregoing, the binder may be PTFE, as well as polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene rubber (SBR), polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefin, polyethylene. Polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (PMMA) (and other acrylic resins), acrylic, polyvinyl acetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide and at least one additional binder selected from poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polybutadiene polymer, polybutadiene rubber (PB), polybutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), polyethyl acrylate (PEA), and combinations thereof.

[0119] [000126] In some embodiments, including any of the foregoing, the cathode active material is a material set forth in International Patent Application Publication No. PCT / US2021 / 049528, filed Sep. 8, 2021, and entitled CATHODE COATING, the entire contents of which are incorporated herein by reference in their entirety for all purposes.

[0120] [000127] In some embodiments, including any of the above, the cathode active material is LiMPO4 (wherein M=Fe, Ni, Co, Mn), Li x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z and LiNixCoyAlzO2, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1.

[0121] [000128] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0122] [000129] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x is 0.8, y is 0.1, and z is 0.1).

[0123] [000130] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x is 0.6, y is 0.2, and z is 0.2).

[0124] [000131] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2 (x is 0.5, y is 0.3, and z is 0.2).

[0125] [000132] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x is 1 / 3, y is 1 / 3, z is 1 / 3).

[0126] [000133] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z It's O2.

[0127] [000134] In some embodiments, including any of the above, the NMC is 0.1 μm <S<50μmの、d 50 The particle size is S.

[0128] [000135] In some embodiments, including any of the above, the NMC is 0.5 μm <S<30μmの、d 50 The particle size is S.

[0129] [000136] In some embodiments, including any of the above, the NMC is 1 μm <S<20μmの、d 50 The particle size is S.

[0130] [000137] In some embodiments, including any of the above, the catholyte is a LSTPS.

[0131] [000138] In some embodiments, including any of the above, the catholyte is arginine.

[0132] [000139] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting sulfide, for example, Li2S-SiS2.

[0133] [000140] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting oxide, for example a lithium loaded garnet.

[0134] [000141] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting halide, such as perovskite.

[0135] [000142] In some embodiments, including any of the foregoing, the catholyte is a lithium ion conducting organic polymer, for example, LiPF6 in PEO.

[0136] [000143] In some embodiments, including any of the above, the catholyte has a particle size of 0.005 μm or less. <T<20μmの、d 50 The particle size is T.

[0137] [000144] In some embodiments, including any of the above, the catholyte has a particle size of 0.01 μm or less. <T<10μmの、d 50 The particle size is T.

[0138] [000145] In some embodiments, including any of the above, the catholyte has a particle size of 0.02 μm or less. <T<5μmの、d 50 The particle size is T.

[0139] [000146] In some embodiments, including any of the above, the mixture has a density of 2 to 2.5 g / cm 3 has a density of

[0140] [000147] In some embodiments, including any of the foregoing, the solvent-free mixture is prepared by mixing binder particles with cathode active material particles and catholyte at a temperature below 0°C.

[0141] [000148] In some embodiments, the PTFE forms fibrils throughout the cathode by allowing the PTFE to form fibrils after cold mixing and during dough kneading (e.g., when the PTFE is in powder form, triclinic crystalline). In some embodiments, this results in a network of PTFE fibers intermingled with the cathode active material. In some embodiments, above room temperature, the PTFE is rubbery, tacky, or sticky, and hexagonal / pseudo-hexagonal.

[0142] Process embodiment A [000149] In some embodiments, a cathode active material (e.g., NMC, 18 g) is mixed with a catholyte (e.g., LSTPS, 3.01 g) to form a mixture. The resulting mixture is mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 8 passes for 20 seconds each.

[0143] [000150] In some embodiments, a binder (e.g., PTFE, 0.201 g) is added to the mixture to form a second mixture. The second mixture is mixed at -7°C using a blade mixer with a rotation speed of 20,000 rpm for 2 passes for 10 seconds each.

[0144] [000151] In some embodiments, the process then includes kneading at room temperature for about 30 minutes.

[0145] [000152] In some embodiments, the process then includes forming the kneaded mixture into a sheet extension using a sheeter.

[0146] Process embodiment B [000153] In some embodiments, a cathode active material (e.g., NMC, 18 g) is mixed with a catholyte (e.g., LSTPS, 3.01 g) to form a mixture. The resulting mixture is mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 8 passes for 20 seconds each.

[0147] [000154] In some embodiments, a binder (e.g., PTFE, 0.201 g) is added to the mixture to form a second mixture. The second mixture is mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 2 passes for 10 seconds each.

[0148] [000155] In some embodiments, the process then includes kneading at about 75°C for about 30 minutes.

[0149] [000156] In some embodiments, the process then includes forming the kneaded mixture into a sheet extension using a sheeter.

[0150] Process embodiment C [000157] In some embodiments, a cathode active material (e.g., NMC, 18 g) is mixed with a catholyte (e.g., LSTPS, 3.01 g) to form a mixture. The resulting mixture is mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 8 passes for 20 seconds each.

[0151] [000158] In some embodiments, a binder (e.g., PTFE, 0.201 g) is added to the mixture to form a second mixture. The second mixture is mixed at -7°C using a blade mixer with a rotation speed of 20,000 rpm for 2 passes for 10 seconds each.

[0152] [000159] In some embodiments, the process then includes kneading at about 75°C for about 30 minutes.

[0153] [000160] In some embodiments, the process then includes kneading at about 45°C for about 30 minutes.

[0154] [000161] In some embodiments, the process then includes forming the kneaded mixture into a sheet extension using a sheeter.

[0155] Process embodiment D [000162] The process illustrated and described in Figures 1 and 2 is also set forth herein.

[0156] [000163] Figure 1 shows an embodiment of a process in which NMC and catholyte materials are mixed with a PTFE binder, then dough mixed, and then subsequently formed into a sheet extrusion using a sheeter, which may also be referred to as an extruder.

[0157] [000164] Figure 1 shows the PTFE agglomerates mixed with NMC particles.

[0158] [000165] Figure 1 shows network formation from PTFE agglomerates mixed with NMC particles as the PTFE forms fibrils and forms a network in the fabric. Figure 1 shows the fabric formed as a sheet.

[0159] [000166] Figure 2 shows another embodiment of the process where NMC and catholyte materials are mixed with a PTFE binder, then dough mixed, and then subsequently formed into sheet extrusions using a sheeter.

[0160] Additional Embodiments [000167] Embodiment 1: A process for manufacturing a solid-state cathode (SSC) sheet, comprising: providing, or having provided, a solvent-free mixture comprising cathode active material particles, catholyte, and binder particles, wherein the binder particles are present at 5 weight percent (w / w) or less; maintaining the mixture at a temperature of about -30°C to -5°C; dough-kneading the mixture to form binder fibrils at a temperature of about 25°C to 200°C; and depositing the mixture to form a SSC sheet.

[0161] [000168] Embodiment 2: The process of embodiment 1, wherein the binder particles are present at 1 w / w% or less.

[0162] [000169] Embodiment 3: The process of embodiment 1 or 2, wherein the binder particles are present at 0.3 w / w% or less.

[0163] [000170] Embodiment 4: The process of any one of embodiments 1-3, comprising maintaining the mixture for 1 to 4 hours.

[0164] [000171] Embodiment 5: The process of any one of embodiments 1-4, comprising maintaining the mixture for 2 hours.

[0165] [000172] Embodiment 6: The process of any one of embodiments 1 to 5, comprising maintaining the mixture at -30°C to -10°C.

[0166] [000173] Embodiment 7: The process of any one of embodiments 1-6, comprising maintaining the mixture at -20°C.

[0167] [000174] Embodiment 8: The process of any one of embodiments 1-7, wherein dough-kneading the mixture to form binder fibrils comprises shearing the binder particles to form binder fibrils.

[0168] [000175] Embodiment 9: The process of any one of embodiments 1 to 8, wherein the temperature of the mixture during dough kneading of the mixture to form binder fibrils is from about 30°C to about 60°C.

[0169] [000176] Embodiment 10: The process of any one of embodiments 1-9, wherein the temperature of the mixture during dough kneading of the mixture to form binder fibrils is about 45°C.

[0170] [000177] Embodiment 11: The process of any one of embodiments 1-10, wherein dough-kneading the mixture to form binder fibrils comprises shearing the cathode active material particles.

[0171] [000178] Embodiment 12: The process of any one of embodiments 1-11, wherein dough-kneading the mixture to form binder fibrils comprises shearing catholyte.

[0172] [000179] Embodiment 13: The process of any one of embodiments 1 to 12, wherein the cathode active material particles are coated cathode active material particles.

[0173] [000180] Embodiment 14: The process of any one of embodiments 1-13, wherein the dough-kneading the mixture to form binder fibrils further comprises compressing the cathode active material particles and the binder particles.

[0174] [000181] Embodiment 15: The process of embodiment 14, further comprising creating a network of binder fibrils throughout the cathode active material particles.

[0175] [000182] Embodiment 16: The process of embodiment 14 or 15, wherein the compressing of the cathode active material particles and the binder particles is at a pressure of 10 MPa to 30 MPa.

[0176] [000183] Embodiment 17: The process of any one of embodiments 1-16, wherein kneading the mixture comprises using a mortar.

[0177] [000184] Embodiment 18: The process of any one of embodiments 1-17, wherein dough kneading the mixture comprises using a twin-screw co-rotating extruder.

[0178] [000185] Embodiment 19: The process of any one of embodiments 1 to 18, further comprising pretreating the binder.

[0179] [000186] Embodiment 20: The process of embodiment 19, wherein the pretreatment comprises atomization of the binder.

[0180] [000187] Embodiment 21: The process of embodiment 20, comprising atomizing the binder using a blade mixer.

[0181] [000188] Embodiment 22: The process of embodiment 20 or 21, comprising atomizing the binder using a blade mixer at about 15°C.

[0182] [000189] Embodiment 23: The process of any one of embodiments 1-22, wherein dough kneading occurs at a temperature of about 21°C to about 31°C.

[0183] [000190] Embodiment 24: The process of any one of embodiments 1-22, wherein dough kneading occurs at a temperature of about 21°C to about 85°C.

[0184] [000191] Embodiment 25: The process of any one of embodiments 1-22, wherein dough kneading occurs at a temperature of from about 31° C. to about 85° C.

[0185] [000192] Embodiment 26: The process of any one of embodiments 1 to 25, wherein the binder is poly(tetrafluoroethylene) (PTFE).

[0186] [000193] Embodiment 27: The process of any one of embodiments 1 to 26, wherein the binder comprises PTFE and further comprises at least one additional binder.

[0187] [000194] Embodiment 28: The cathode active material is LiMPO4 (M=Fe, Ni, Co, Mn); Li x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z O2 (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1); and LiNi x Co y Al z 28. The process of any one of the preceding embodiments, wherein the aryl group is selected from the group consisting of aryl, aryl, aryl and aryl. O2, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1.

[0188] [000195] Embodiment 29: The cathode active material is LiNi x Mn y Co z 29. The process of any one of embodiments 1 to 28, wherein O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0189] [000196] Embodiment 30: The cathode active material is LiNi x Mn y Co z30. The process of embodiment 29, wherein O2 is O2, where x is 0.8, y is 0.1, and z is 0.1.

[0190] [000197] Embodiment 31: The cathode active material is LiNi x Mn y Co z 30. The process of embodiment 29, wherein O2 is O2, where x is 0.6, y is 0.2, and z is 0.2.

[0191] [000198] Embodiment 32: The cathode active material is LiNi x Mn y Co z 30. The process of embodiment 29, wherein O2 is O2, where x is 0.5, y is 0.3, and z is 0.2.

[0192] [000199] Embodiment 33: The cathode active material is LiNi x Mn y Co z 30. The process of embodiment 29, wherein said first is O2 (x is 1 / 3, y is 1 / 3, and z is 1 / 3).

[0193] [000200] Embodiment 34: The process of embodiment 29, wherein the cathode active material is Li(NiCoMn)O2.

[0194] [000201] Embodiment 35: The cathode active material has a d 50 The process of any one of embodiments 29 to 34, having a particle size, S.

[0195] [000202] Embodiment 36: The NMC has a d 50 36. The process of any one of embodiments 29 to 35, having a particle size, S.

[0196] [000203] Embodiment 37: The NMC has a d 50 37. The process of any one of embodiments 29 to 36, having a particle size, S.

[0197] [000204] Embodiment 38: The NMC has a d 50 38. The process of any one of embodiments 29 to 37, having a particle size, S.

[0198] [000205] Embodiment 39: The NMC has a d 50 39. The process of any one of embodiments 29 to 38, having a particle size, S.

[0199] [000206] Embodiment 40: The NMC has a d 50 40. The process of any one of embodiments 29 to 39, having a particle size, S.

[0200] [000207] Embodiment 41: The catholyte has a particle size of 0.02 μm. <T<5μmの、d 50 41. The process of any one of the preceding embodiments, having a particle size, T.

[0201] [000208] Embodiment 42: The catholyte has a particle size of 0.05 μm. <T<3μmの、d 50 42. The process of any one of the preceding embodiments, having a particle size, T.

[0202] [000209] Embodiment 43: The catholyte has a particle size of 0.1 μm. <T<1.5μmの、d 50 43. The process of any one of the preceding embodiments, having a particle size, T.

[0203] [000210] Embodiment 44: After the mixture is thinned into a solid-state cathode sheet, the mixture has a density of 2 to 2.5 g / cm 3 44. The process of any one of the preceding embodiments, wherein the granules have a density of

[0204] [000211] Embodiment 45: The process of any one of embodiments 1 to 44, wherein the solvent-free mixture is produced by mixing the binder particles with the cathode active material particles and the catholyte at a temperature below 0°C.

[0205] [000212] Embodiment 46: The process of any one of embodiments 1 to 45, comprising calendering the SSC at a line pressure ranging from 0.5 tons / cm to 10 tons / cm.

[0206] [000213] Embodiment 47: The process of any one of embodiments 1 to 46, wherein the binder fibrils are less than 1 mm in length.

[0207] [000214] Embodiment 48: The process of any one of embodiments 1 to 47, wherein the SSC has a porosity in the range of 40 volume % to 50 volume % (v / v) prior to compressing the cathode active material particles and binder particles.

[0208] [000215] Embodiment 41: The process of any one of embodiments 1-48, wherein the SSC has a porosity in the range of less than 40 v / v % prior to compressing the cathode active material particles and the binder particles.

[0209] [000216] Embodiment 50: The process of any one of embodiments 1 to 49, wherein the SSC has a durometer range of 40 to 80 prior to compressing the cathode active material particles and the binder particles.

[0210] [000217] Embodiment 51: The process of any one of embodiments 1 to 50, wherein the SSC has a fabric density after thinning into a sheet of 2 to 2.5 g / cc.

[0211] [000218] Embodiment 52: A solid-state cathode produced by the process of any one of embodiments 1 to 51.

[0212] [000219] Embodiment 53: The solid-state cathode of embodiment 52, wherein the average tensile strength is about 0.3 MPa to 0.5 MPa.

[0213] [000220] Embodiment 54: The solid-state cathode of embodiment 52, wherein the average tensile strength is about 0.45 MPa.

[0214] [000221] Embodiment 55: The solid-state cathode of embodiment 52, wherein the average Young's modulus is about 0.5 GPa to 0.8 GPa.

[0215] [000222] Embodiment 56: The solid-state cathode of embodiment 52, wherein the average Young's modulus is about 0.7 GPa.

[0216] [000223] Embodiment 57: The solid-state cathode of embodiment 52, wherein the average plastic elongation is about 5% to 15%.

[0217] [000224] Embodiment 58: The solid-state cathode of embodiment 52, wherein the average plastic elongation is about 10%.

[0218] [000225] Embodiment 59: The solid-state cathode of embodiment 52, wherein the average plastic elongation is about 9%.

[0219] [000226] Embodiment 60: The solid-state cathode of embodiment 52, wherein the average plastic elongation is about 8%.

[0220] [000227] Embodiment 61: The solid-state cathode of embodiment 52, wherein the elasticity is in the range of 0.01 to 0.15 GPa. In these embodiments, the solid-state cathode sheet is less than 1 mm thick. In some of these embodiments, the solid-state cathode sheet is at least 100 nm thick. In some of these embodiments, the solid-state cathode sheet is at least 250 nm thick. In some of these embodiments, the solid-state cathode sheet is at least 500 nm thick. In some of these embodiments, the solid-state cathode sheet is at least 1 μm thick.

[0221] [000228] Embodiment 62: A composition comprising: cathode active material particles; a binder present at 1 w / w% or less, wherein the binder is mixed with the cathode active material particles; the binder is present as fibrils; and the composition is solvent-free.

[0222] [000229] Embodiment 63: The composition of embodiment 62, wherein the binder is present at 0.3 w / w% or less.

[0223] [000230] Embodiment 64: The composition of embodiment 62 or 63, wherein the binder is PTFE.

[0224] [000231] Embodiment 65: The composition of any one of embodiments 62-64, wherein the binder comprises PTFE and further comprises at least one additional binder. In some embodiments, the additional binder is selected from the group consisting of polypropylene (PP), polyethylene, atactic polypropylene (aPP), isotactic polypropylene (iPP), ethylene propylene rubber (EPR), ethylene pentene copolymer (EPC), polyisobutylene (PIB), styrene butadiene rubber (SBR), polyolefin, polyethylene-co-poly-1-octene (PE-co-PO), polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylic, polyvinyl acetacetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylene, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymer, silicone, and the like.In some examples, including any of the foregoing, the binder is a polymer and may be polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinylpyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxyethoxyethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxyethoxyethyl glycidyl The polymer is selected from the group consisting of poly(allyl glycidyl ether) (PEO-MEEGE-AGE), polysiloxane, polyvinylidene fluoride (PVDF), polyvinylidene hexafluoropropylene fluoride (PVDF-HFP), ethylene propylene (EPR), nitrile rubber (NPR), styrene-butadiene rubber (SBR), polybutadiene polymer, polybutadiene rubber (PB), polyisobutadiene rubber (PIB), polyolefin, alpha-polyolefin, ethylene alpha-polyolefin, polyisoprene rubber (PI), polychloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and polyethyl acrylate (PEA).

[0225] [000232] Embodiment 66: The cathode active material is LiMPO4 (M=Fe, Ni, Co, Mn); Li x Ti y O z (wherein x is 0 to 8, y is 1 to 12, and z is 1 to 24); LiMn 2a Ni a O4 (wherein a is 0 to 2); nickel cobalt aluminum oxide; LiNi x Mn y Co z O2 (x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1); and LiNi x Co y Al z The composition of any one of embodiments 62-65, wherein the compound is selected from the group consisting of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27,

[0226] [000233] Embodiment 67: The cathode active material is LiNi x Mn y Co z The composition of any one of embodiments 62-66, wherein O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0227] [000234] Embodiment 68: The cathode active material is LiNi x Mn y Co z The composition of embodiment 67, wherein the compound is O2, wherein x is 0.8, y is 0.1, and z is 0.1.

[0228] [000235] Embodiment 69: The cathode active material is LiNi x Mn y Co z The composition of embodiment 67, wherein the compound is O2, wherein x is 0.6, y is 0.2, and z is 0.2.

[0229] [000236] Embodiment 70: The cathode active material is LiNi x Mn y Co z The composition of embodiment 67, wherein X is 0.5, Y is 0.3, and Z is 0.2.

[0230] [000237] Embodiment 71: The cathode active material is LiNi x Mn y Co z The composition of embodiment 67, wherein X is 1 / 3, Y is 1 / 3, and Z is 1 / 3.

[0231] [000238] Embodiment 72: The composition of embodiment 67, wherein the cathode active material is Li(NiCoMn)O2.

[0232] [000239] Embodiment 73: The NMC has a d50 73. The composition of any one of embodiments 67-72, having a particle size, S.

[0233] [000240] Embodiment 74: The NMC has a thickness of 1 μm. <S<20μmの、d 50 74. The composition of any one of embodiments 67-73, having a particle size, S.

[0234] [000241] Embodiment 75: The NMC is 4 μm <S<20μmの、d 50 75. The composition of any one of embodiments 67-74, having a particle size, S.

[0235] [000242] Embodiment 76: The NMC has a thickness of 2 μm. <S<15μmの、d 50 76. The composition of any one of embodiments 67-75, having a particle size, S.

[0236] [000243] Embodiment 77: The NMC has a thickness of 4 μm. <S<10μmの、d 50 77. The composition of any one of embodiments 67-76, having a particle size, S.

[0237] [000244] Embodiment 78: The catholyte has a particle size of 0.02 μm. <T<5μmの、d 50 78. The composition of any one of embodiments 67-77, having a particle size, T.

[0238] [000245] Embodiment 79: The catholyte has a particle size of 0.05 μm. <T<3μmの、d 50 The composition of any one of embodiments 67-78, having a particle size, T.

[0239] [000246] Embodiment 80. The composition of any one of embodiments 62-79, further comprising catholyte, wherein the catholyte has a particle size of 0.02 μm or less. <T<5μmの、d 50 A composition having a particle size, T.

[0240] [000247] Embodiment 81: The composition of any one of embodiments 62-80, further comprising catholyte, wherein the catholyte has a particle size of 0.05 μm or less. <T<3μmの、d 50 A composition having a particle size, T.

[0241] [000248] Embodiment 82: The composition of any one of embodiments 62-81, further comprising catholyte, wherein the catholyte has a particle size of 0.1 μm or less. <T<1.5μmの、d 50 A composition having a particle size, T.

[0242] [000249] Embodiment 83: The composition has a density of 2 to 2.5 g / cm 3 83. The composition of any one of embodiments 36-82, having a density of

[0243] [000250] Embodiment 84: A thin sheet comprising the composition of any one of embodiments 62-83.

[0244] [000251] Embodiment 85: The thin sheet of embodiment 84, wherein the porosity is less than 40 v / v%.

[0245] [000252] Embodiment 86: The cathode active loading is 1 to 15 mAh / cm 2 85. The thin sheet of embodiment 84, wherein

[0246] [000253] Embodiment 87: The cathode active loading is at least 5 mAh / cm 2 85. The thin sheet of embodiment 84, wherein

[0247] [000254] Embodiment 88: A thin sheet according to any one of embodiments 84 to 87, wherein the sheet has a thickness of 120 μm.

[0248] [000255] Embodiment 89: A thin sheet according to any one of embodiments 84 to 88, wherein the sheet has a thickness of 150 μm.

[0249] [000256] Embodiment 90: The thin sheet of any one of embodiments 84-89, wherein the sheet is at least 5 centimeters (cm) wide.

[0250] [000257] Embodiment 91: A thin sheet according to any one of embodiments 84 to 90, wherein the sheet is at least 1 meter (m) wide.

[0251] [000258] Embodiment 92: A thin sheet according to any one of embodiments 84 to 91, wherein the sheet is at least 10 cm in length.

[0252] [000259] Embodiment 93: A thin sheet according to any one of embodiments 84 to 92, wherein the sheet is at least 70 cm in length.

[0253] [000260] Embodiment 94: A thin sheet according to any one of embodiments 84 to 93, wherein the sheet is at least 1 m in length.

[0254] [000261] Embodiment 95: A bilayer comprising a metal layer in contact with the thin sheet of any one of embodiments 62-94.

[0255] [000262] Embodiment 96: A trilayer comprising a metal layer between and in contact with two thin sheets according to any one of embodiments 84-94.

[0256] [000263] Embodiment 97: The bilayer or trilayer of any one of embodiments 94-96, wherein the metal layer is an Al layer.

[0257] [000264] Embodiment 98: The bilayer or trilayer of any one of embodiments 94-96, wherein the metal layer is a Ni layer.

[0258] [000265] Embodiment 99: The bilayer or trilayer of any one of embodiments 94-96, wherein the metal layer is a layer of Cu, Ni, Al, Mg, Ag, Au, Pt, or a combination thereof.

[0259] [000266] Embodiment 100: A bilayer comprising a solid-state electrolyte layer in contact with the thin sheet of any one of embodiments 84-94.

[0260] [000267] Embodiment 101: A trilayer comprising a solid-state electrolyte layer between and in contact with two thin sheets of any one of embodiments 84-94.

[0261] [000268] Embodiment 102: The bilayer or trilayer of any one of embodiments 100-101, wherein the solid-state electrolyte layer is a layer of lithium-filled garnet.

[0262] [000269] In some embodiments, presented herein is a process for manufacturing a solid-state cathode (SSC) sheet, the process including providing, or having provided, a solvent-free mixture including cathode active material particles, catholyte, and binder particles (wherein the binder particles are present at 5 weight percent (w / w) or less); maintaining the mixture at a temperature of about -30°C to -5°C; dough-kneading the mixture to form binder fibrils at a temperature of about 25°C to 200°C; and depositing the mixture to form an SSC sheet, thereby producing an SSC sheet.

[0263] [000270] In some embodiments, including any of the foregoing, the process includes mixing the cathode active material particles with catholyte and binder particles before maintaining the mixture.

[0264] [000271] In some embodiments, including any of the foregoing, the process includes mixing the mixture while maintaining the mixture at a temperature of about -30°C to -5°C.

[0265] [000272] In some embodiments, including any of the above, the binder particles are present at 1 w / w% or less.

[0266] [000273] In some embodiments, including any of the above, the process includes maintaining the mixture for 1 hour to 4 hours.

[0267] [000274] In some embodiments, including any of the above, the process includes maintaining the mixture at a temperature of from -30°C to -10°C.

[0268] [000275] In some embodiments, including any of the foregoing, dough-kneading the mixture to form binder fibrils includes shearing the binder particles to form the binder fibrils.

[0269] [000276] In some embodiments, including any of the above, the temperature of the mixture during dough kneading of the mixture to form binder fibrils is about 30°C to about 60°C.

[0270] [000277] In some embodiments, including any of the foregoing, dough-kneading the mixture to form binder fibrils includes shearing the catholyte.

[0271] [000278] In some embodiments, including any of the foregoing, the cathode active material particles are coated cathode active material particles.

[0272] [000279] In some embodiments, including any of the foregoing, dough-kneading the mixture to form binder fibrils further includes compressing the cathode active material particles and the binder particles.

[0273] [000280] In some embodiments, including any of the above, the cathode active material particles and binder particles are at a pressure of from 10 MPa to 30 MPa.

[0274] [000281] In some embodiments, including any of the above, the binder is poly(tetrafluoroethylene) (PTFE).

[0275] [000282] In some embodiments, including any of the above, the binder comprises PTFE and further comprises at least one additional binder.

[0276] [000283] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0277] [000284] In some embodiments, including any of the above, the cathode active material has a d 50 The particle size is S.

[0278] [000285] In some embodiments, including any of the above, the SSC further comprises catholyte, the catholyte having a particle size of 0.02 μm. <T<5μmの、d 50 The particle size is T.

[0279] [000286] In some embodiments, including any of the above, the SSC sheet has a compressibility of 2 to 2.5 g / cm 3 has a density of

[0280] [000287] In some embodiments, including any of the foregoing, the process includes calendering the SSC at a line pressure in the range of 0.5 tons / cm to 10 tons / cm.

[0281] [000288] In some embodiments, including any of the above, the binder fibrils are less than 1 mm in length.

[0282] [000289] In some embodiments, including any of the above, the SSC has a porosity in the range of 40% to 50% by volume (v / v) prior to compressing the cathode active material particles and binder particles.

[0283] [000290] In some embodiments, including any of the foregoing, the SSC has a porosity in the range of less than 40 v / v % after compressing the cathode active material particles and binder particles.

[0284] [000291] In some embodiments, including any of the foregoing, mixing to form the binder fibrils occurs at a temperature of about 35°C to 100°C.

[0285] [000292] In some embodiments, including any of the foregoing, mixing to form the binder fibrils occurs at a temperature of about 35°C to 75°C.

[0286] [000293] In some embodiments, including any of the foregoing, dough kneading of the mixture to form binder fibrils occurs at a temperature of about 35°C to 50°C.

[0287] [000294] Presented herein, in some embodiments, is a solid state cathode sheet produced by the processes herein.

[0288] [000295] In some embodiments, including any of the above, the solid-state cathode sheet has an average tensile strength that is from about 0.3 MPa to about 0.5 MPa.

[0289] [000296] In some embodiments, including any of the above, the solid-state cathode sheet has an average Young's modulus that is from about 0.5 GPa to about 0.8 GPa.

[0290] [000297] In some embodiments, including any of the above, the solid-state cathode sheet has an average plastic elongation that is from about 5% to about 15%.

[0291] [000298] In some embodiments, including any of the above, the solid-state cathode sheet has an elasticity that is about 0.01 GPa to about 0.15 GPa. In some embodiments, the elasticity can be influenced by modifying the dispersion of the binder (e.g., PTFE). In some embodiments, the elasticity can be influenced by modifying the kneading process.

[0292] [000299] In some embodiments, provided herein are compositions that include cathode active material particles; and a binder present at 1 w / w% or less, where the binder is mixed with the cathode active material particles; the binder is present as fibrils; and the composition is solvent-free.

[0293] [000300] In some embodiments, including any of the above, the composition further comprises catholyte.

[0294] [000301] In some embodiments, including any of the above, the binder is poly(tetrafluoroethylene) (PTFE).

[0295] [000302] In some embodiments, including any of the above, the binder comprises PTFE and further comprises at least one additional binder.

[0296] [000303] In some embodiments, including any of the above, the cathode active material is LiNi x Mn y Co z O2(x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1), where x+y+z=1.

[0297] [000304] In some embodiments, including any of the above, the NMC has a d 50 The particle size is S.

[0298] [000305] In some embodiments, including any of the above, the catholyte has a particle size of 0.02 μm or less. <T<5μmの、d 50 The particle size is T.

[0299] [000306] In some embodiments, including any of the above, the composition, when formed into a sheet, has a density of 2 to 2.5 g / cm 3 has a density of

[0300] [000307] In some embodiments, including any of the above, the binder fibrils are less than 1 mm in length.

[0301] [000308] In some embodiments, including any of the above, the SSC has a porosity in the range of less than 40 v / v %.

[0302] [000309] Presented herein, in some embodiments, are thin sheets comprising the compositions provided herein.

[0303] [000310] In some embodiments, a bilayer is provided herein that includes a metal layer in contact with a thin sheet as provided herein.

[0304] [000311] In some embodiments, a tri-layer is provided herein that includes a metal layer between and in contact with two thin sheets as provided herein.

[0305] [000312] In some embodiments, including any of the above, the metal layer is a layer of Al, Ni, Cu, Ni, Al, Mg, Ag, Au, Pt, or a combination thereof.

[0306] [000313] In some embodiments, a bilayer is provided herein that includes a solid state electrolyte layer in contact with a thin sheet as provided herein.

[0307] [000314] In some embodiments, a trilayer is provided herein that includes a solid state electrolyte layer between and in contact with two thin sheets of the material provided herein.

[0308] [000315] In some embodiments, including any of the foregoing, the solid-state electrolyte layer is a layer of lithium-filled garnet. EXAMPLES

[0309] Working Example [000316] Reagents, chemicals, and raw materials were purchased commercially unless otherwise stated to the contrary.

[0310] [000317] Pouch cell containers were purchased from Showa Denko.

[0311] [000318] The electrochemical potentiostat used was an Arbin potentiostat.

[0312] [000319] Electrical impedance spectroscopy (EIS) was performed using a Biologic VMP3, VSP, VSP-300, SP-150, or SP-200.

[0313] [000320] Electron microscopy was performed on an FEI Quanta SEM, Helios 600i, or Helios 660 FIB-SEM.

[0314] [000321] Transmission electron microscopy was performed as follows.

[0315] [000322] Sample preparation: Samples for TEM measurements were prepared using a Ga ion source focused ion beam (nanoDUE'T NB5000, Hitachi High-Technologies). To protect the surface of the material from the Ga ion beam, multiple protective layers were deposited prior to sampling; first, a metal layer was deposited by plasma coater, then a carbon protective layer and a tungsten layer were deposited by high vacuum evaporation and focused ion beam, respectively. Thin slice sampling was performed by focused ion beam. The prepared samples were measured in the TEM.

[0316] [000323] TEM measurements: TEM images of the coated NMC were obtained by a field emission electron microscope (JEM-2100F, JEOL). The accelerating voltage was set at 200 kV. The electron beam radius was set at about 0.7-1 nm.

[0317] [000324] X-ray powder diffraction (XRD) was performed on a Bruker D8 Advance A25 with Cu K-alpha radiation at room temperature (e.g., 21°C to 23°C). Source is Cu-Ka, wavelength at 1.54 Å. X-ray at 40 kV and 25 mA. Detector: LYNXEYE_XE with PSD opening 2.843. Fixed divergence slit at 0.6 mm and anti-scatter at 5.0 mm.

[0318] [000325] Milling was performed using a Retsch PM 400 Planetary Ball Mill. Mixing was performed using a Fischer Scientific vortex mixer, a Flaktek speed mixer, or a Primix film homogenizer.

[0319] [000326] Casting was done on a TQC drawdown table. Calendering was done on an IMC calender.

[0320] [000327] Light scattering was performed on a Horiba, Model: Partica, Model Number: LA-950V2, General Term: Laser Scattering Particle Size Distribution Analyzer.

[0321] [000328] The lithium nickel cobalt manganese oxide (NMC) used in the examples is LiNi 0.85 Co 0.1 Mn 0.05 It was O2.

[0322] Example 1 - Preparation of solid state cathode sheet [000329] Step 1: 18 g of NMC was mixed with 3.01 g of LSTPS. The resulting mixture was mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 8 passes, 20 seconds per pass. 10 S 0.5 Sn 0.5 P2S 12 (hereinafter referred to as "LSTPS") is wet milled to a thickness of about 50 nm to 500 nm. 50 This resulted in LSTPS particles having a particle size of 1.0 mm, see U.S. Patent Nos. 9,172,114 and 10,535,878, which are incorporated by reference in their entireties for all purposes.

[0323] [000330] Step 2: 0.201 g of PTFE was added to the mixture.

[0324] [000331] Step 3: The resulting mixture was mixed at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 2 passes for 10 seconds each.

[0325] [000332] Step 4: The resulting mixture was dough kneaded at room temperature.

[0326] [000333] Step 5: The resulting mixture was formed into a sheet extrusion using a sheeter. The use of the term sheeter is synonymous with the term extruder herein.

[0327] Example 2 - Analysis of solid state cathode sheets [000334] Differential scanning calorimetry was used to analyze the PTFE fibrillation process. See Figure 3. Figure 3 shows that there is an advantage to PTFE being dispersed at a temperature below the triclinic to hexagonal phase transition temperature. In this example, the phase transition temperature was 15°C. Figure 3 shows that there is an advantage to compounding at a temperature above the phase transition temperature.

[0328] [000335] DSC was measured on PTFE alone to determine the phase transition temperature. Figure 3 shows that mixing of PTFE may need to occur at that temperature and below the exotherm peak; mixing should occur after the onset of the exotherm peak.

[0329] [000336] Differential scanning calorimetry was performed using a STA 449 F3 Jupiter, Netzsch system scanning between (-10°C) and (70°C) at a scan rate of 2°C / min using closed Au-plated SS pans sealed under a dry air atmosphere (dew point = -50°C).

[0330] Example 3: Cycling test [000337] Solid electrolytes were prepared: Lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium iodide (LiI) were mixed in the desired ratios. In one sample, lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium iodide (LiI) were mixed. The molar ratio of LiI:Li2S:P2S5 was (3-4):(0.1-1):(0.5-1.5). The mixture was placed in a 500 ml zirconia milling jar with 1 mm zirconia milling media at a milling media:powder mass ratio of >7.5. The mixture was agitated in a planetary mill (Retsch PM400, 150 mm radius of rotation, 1:2 speed ratio) for 16-36 (16-32) hours.

[0331] [000338] An all solid-state battery was fabricated using a solid-state cathode as fabricated in Example 1 and a separator made from the solid electrolyte in the previous section.

[0332] [000339] The cathode layer and separator were pressed at 700 MPa to densify the two into a pellet-type battery. An aluminum current collector was used adjacent to the cathode layer. A nickel current collector was used adjacent to the anode layer. Finally, the stack of pellets and current collectors was vacuum sealed in a Mylar bag as a battery cell. The anode layer was composed of lithium metal. When the battery cell was charged, metallic lithium was plated as the anode. The cathode layer was a solid-state sheet that was 100 μm to 150 μm thick. The solid-state separator layer was 30 μm to 50 μm thick.

[0333] [000340] The battery was cycled and the results are shown in Figure 4.

[0334] Example 4: Area Specific Resistivity (ASR) Test [000341] A solid electrolyte was prepared: Lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium iodide (LiI) were mixed in a given ratio. In one sample, lithium sulfide (Li2S), phosphorus pentasulfide (P2S5), and lithium iodide (LiI) were mixed. The molar ratio of LiI:Li2S:P2S5 was (3-4):(0.1-1):(0.5-1.5). The mixture was placed in a 500 ml zirconia milling jar with 1 mm zirconia milling media at a milling media:powder mass ratio of >7.5. The mixture was agitated in a planetary mill (Retsch PM400, 150 mm radius of rotation, 1:2 speed ratio) for sixteen to thirty-two (16-32) hours.

[0335] [000342] An all solid-state battery was fabricated using a solid-state cathode as fabricated in Example 1 and a separator made of the solid electrolyte as prepared in the previous section. The cathode layer was a solid shared sheet that was 100 μm to 150 μm thick. The solid-state separator layer was 30 μm to 50 μm thick.

[0336] [000343] The cathode layer and separator were pressed at 700 MPa to densify the two into a pellet-type battery. An aluminum current collector was used adjacent to the cathode layer. A nickel current collector was used adjacent to the anode layer. Finally, the stack of pellets and current collectors was vacuum sealed into a Mylar bag to be the battery cell. The anode layer was composed of lithium metal. When the battery cell was charged, metallic lithium was plated as the anode.

[0337] [000344] The battery cell is driven at 0.55mA / cm 2 The cells were charged and discharged at 30°C with intermittent current pulses at a constant current density of (C / 10 rate) and within the operating voltage of 3 V to 4.25 V. The current pulses were applied for 9 min, the current was stopped, and the system was allowed to relax for 3 min. This intermittent pulse was repeated until the cell voltage reached 4.25 V during charging and 3 V during discharging. The area specific resistance (ASR) of the battery cell was obtained by reading the voltage drop during the relaxation step during discharging. The obtained ASR was named R1.

[0338] [000345] After cycling at 30°C, the battery cell was again cycled at 1.7mA / cm 2 The battery cell was charged to 4.25 V at a current density of 1000 mAh. The temperature of the cell was then increased to 60° C. After the temperature stabilized at 60° C., the battery cell was held at 4.25 V for 7 days and the cell was discharged to 3 V.

[0339] [000346] The temperature of the battery cell was lowered to 30°C. The battery cell was charged between 3V and 4.25V and 1.7mA / cm 2 The battery was charged and discharged at a current density of 1000 mA / s, from which the ASR (R2) was determined.

[0340] [000347] Stability was evaluated by ΔR=R2-R1, and the results are shown in Figure 5.

[0341] Example 5: Tensile strength test [000348] An all solid state cathode sheet was prepared as in Example 1 using an extruder.

[0342] [000349] The tensile strength of the cathode sheet as a function of strain was tested for a series of samples, and the results are shown in Figure 6.

[0343] [000350] An Instron mechanical tester with 100N load cell and pneumatic side action grips was used to perform the tensile tests. The test speed was 1m / min. The difference between the two groups of samples was the dough processing procedure. Higher strength and ductility were observed, indicating the importance of the cold PTFE dispersion and warm dough mixing.

[0344] Example 6 - Preparation of solid state cathode sheet [000351] Step 1: Add 18 g of NMC to 3.01 g of Li 10 S 0.5 Sn 0.5 P2S 12 (hereinafter referred to as "LSTPS" in this specification). The resulting mixture was mixed at room temperature for 8 passes, 20 seconds per pass, using a blade mixer at a rotation speed of 20,000 rpm. LSTPS was wet milled as in Example 1 to obtain a diameter of about 50 nm to 500 nm. 50 This resulted in LSTPS particles having a particle size of 1.0 mm.

[0345] [000352] Step 2: 0.201 g of PTFE was added to the mixture. The PTFE had a PTFE powder size of 1 μm with particles of PTFE smaller than 1 μm.

[0346] [000353] Step 3: The resulting mixture was stabilized at about -20°C for at least 2 hours. The stabilized mixture was then mixed 10 times, 2 seconds per time, using a blade mixer with a rotation speed of 20,000 rpm. Between each mixing time, the mixture was returned to the -20°C environment and stabilized for 2 minutes.

[0347] [000354] Step 4: The resulting mixture was removed from the -20°C environment. Then, fibrillation was carried out in a kneader at 45°C.

[0348] [000355] Step 5: The resulting mixture was formed into a sheet extrusion using a sheeter, also known as an extruder.

[0349] [000356] Step 6: The sheet was densified at high pressure by calendering. The calendering had a line pressure of 0.5 tons / cm to 10 tons / cm.

[0350] Example 7 - Comparison of cathode preparations [000357] Three exemplary cathodes were prepared by the method in Example 6, with modifications as discussed below. Three exemplary cathodes were prepared by varying the conditions in steps 3 and 4 of Example 6 as follows.

[0351] [000358] Group 1 was prepared by mixing the stabilized mixture at -30°C using a blade mixer with a rotation speed of 20,000 rpm for 10 times, 2 seconds per time. The samples were stabilized frequently during the mixing process. After mixing at -30°C, fibrillation was then carried out in a kneader at 160°C.

[0352] [000359] Group 2 was prepared by mixing the stabilized mixture 10 times for 2 seconds each time using a blade mixer with a rotation speed of 20,000 rpm at temperatures ranging from -20°C to 0°C. After mixing at -20°C to 0°C, fibrillation was then carried out in a kneader at 45°C.

[0353] [000360] Group 3 was prepared by mixing the stabilized mixture at room temperature using a blade mixer with a rotation speed of 20,000 rpm for 10 passes, 2 seconds each. After mixing at -20°C to 0°C, fibrillation was then carried out in a kneader at room temperature.

[0354] [000361] For the three groups of samples, the properties of the solid state cathode sheets produced according to Example 6 and detailed herein and deposited as sheets were as follows: Average tensile strength for each group: ○ Group 1=0.84MPa, ○ Group 2=0.44MPa, ○ Group 3=0.18MPa. Average elastic modulus for each group: ○ Group 1=0.10GPa, ○ Group 2=0.07GPa, ○ Group 3=0.02GPa. Average plastic elongation for each group: ○ Group 1=18%, ○ Group 2=8.7%, ○ Group 3=1.7%.

[0355] [000362] Sample properties are shown in Figures 7 and 8.

[0356] [000363] Tensile strength was measured using an Instron mechanical tester with a 100N load cell and pneumatic side action grips to perform the tensile test. The test speed was 1 m / min.

[0357] [000364] Uncontrolled PTFE dispersion / compounding temperatures can lead to soft, weak, and brittle SSC sheets that are difficult to handle.

[0358] [000365] Cold PTFE dispersion and hot SSC compounding resulted in SSC sheets that were significantly stronger, stiffer, and more ductile. This is shown by the cluster identified as Group 2 in the center of Figures 7 and 8. Group 2 was unexpectedly advantageous with respect to its average tensile strength, average elastic modulus, and average plastic elongation, as noted above and herein.

[0359] [000366] In some cases where the sheet is too stiff and strong, such as in group 3, this can cause difficulties in the sheet thinning process. Challenges also exist when the sheet is brittle and weak, such as in group 1.

[0360] [000367] The results suggest that plastic elongation is an important feature since the minimum desired product would be a brittle SSC dough sheet. This would be associated with low plastic elongation. If the tensile strength and modulus of the material are too high, the SSC thinning process would be more difficult. For example, the dough may be too stiff and / or too hard.

[0361] [000368] The embodiments and examples described above are intended to be merely illustrative and not limiting. Those skilled in the art will recognize, or be able to ascertain, the use of no more than routine experimentation, numerous equivalents to the specific compounds, raw materials, and procedures. All such equivalents are considered to be within the scope of, and are encompassed by, the appended claims.

Claims

1. A manufacturing process for solid-state cathode (SSC) sheets, To provide, or to provide, a solvent-free mixture comprising cathode active material particles, catholite, and binder particles (wherein the binder particles are present in an amount of 5 wt percent (w / w) or less, and the binder particles are poly(tetrafluoroethylene) (PTFE); The mixture is mixed while maintaining the mixture at a temperature below 20°C; The mixture is kneaded into a dough at a temperature of approximately room temperature to 200°C to form binder fibrils; The aforementioned mixture is deposited to form an SSC sheet; This allows us to manufacture SSC sheets. A process that includes this.

2. The process according to claim 1, wherein the dough kneading of the mixture for forming binder fibrils comprises shearing the binder particles to form binder fibrils.

3. The process according to claim 1, wherein the dough kneading of the mixture for forming binder fibrils further comprises compressing the cathode active material particles and binder particles.

4. The process according to claim 3, wherein the compression of the cathode active material particles and binder particles is performed at a pressure of 10 MPa to 30 MPa.

5. The process according to any one of claims 1 to 4, comprising calendering the SSC at a line pressure in the range of 0.5 ton / cm to 10 ton / cm.

6. The process according to any one of claims 1 to 4, wherein the binder fibril has a length greater than 0 mm and less than 1 mm.

7. The process according to any one of claims 1 to 4, wherein the SSC has a porosity in the range of 40 volume% to 50 volume% (v / v) before compressing the cathode active material particles and binder particles.

8. The process according to any one of claims 1 to 4, wherein the cathode active material is LiNi x Mn y Co z O 2, x + y + z = 1, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1, where x + y + z = 1.

9. The process according to any one of claims 1 to 4, wherein the catholite is LSTPS or silver-germanium sulfide.

10. A solid cathode sheet manufactured by the process described in any one of claims 1 to 4.

11. The solid-state cathode sheet according to claim 10, wherein the average tensile strength is approximately 0.3 MPa to approximately 0.5 MPa.

12. The solid-state cathode sheet according to claim 10, wherein the average Young's modulus is about 0.5 GPa to about 0.8 GPa.

13. The solid state cathode sheet according to claim 10, wherein the average plastic elongation is about 5% to about 15%.

14. Cathode active material particles and; Binder present at 1 w / w% or less; Cassolite and A solid-state cathode composition comprising, The binder is poly(tetrafluoroethylene) (PTFE), The binder is mixed with the cathode active material particles; The binder exists as fibrils, and the fibrils have a length greater than 0 and less than 1 mm; The composition does not contain a solvent. composition.

15. The cathode active material is LiNi ｘ Mn ｙ Co ｚ O ２ The solid-state cathode composition according to claim 14, wherein x + y + z = 1, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, and 0 ≤ z ≤ 1, where x + y + z = 1.

16. The composition is concentrated in a sheet at a concentration of 2 to 2.5 g / cm². ３ The solid-state cathode composition according to claim 14, having the density of .

17. The solid-state cathode composition according to claim 14, wherein the SSC has a porosity in the range of more than 0 v / v% and less than 40 v / v%.

18. The solid state cathode composition according to any one of claims 14 to 17, wherein the average tensile strength is about 0.3 MPa to about 0.5 MPa.

19. The solid-state cathode composition according to any one of claims 14 to 17, wherein the average Young's modulus is about 0.5 GPa to about 0.8 GPa.

20. The solid state cathode composition according to any one of claims 14 to 17, wherein the catholite is LSTPS or silver-germanium sulfide ore.

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