Cathode compositions and processes for making and using the same

Abstract

Set forth herein are compositions and processes for making cathode slurries and dried, solid-state cathodes. These cathodes are useful for high-energy lithium metal secondary batteries.

Description

CATHODE COMPOSITIONS AND PROCESSES FOR MAKING AND USING THE SAMECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority- to. and the benefit of, U.S. Provisional Patent Application No. 63 / 660,626, filed June 17, 2024, the entire contents of which are herein incorporated by reference in its entirety- for all purposes.TECHNICAL FIELD

[0002] The instant disclosure relates to rechargeable batteries and related cathode compositions.BACKGROUND

[0003] Cathodes made with slurries that include cathode active materials having high amounts of Ni, such as NMC 811 and residual lithium salts tend to react with moisture to generate Li2CO? and LiOH. Li2CO3 and LiOH then cause the cathode slurry to have a high pH. The high pH (re., basic slurry) can result in some binders, such as polyvinylidene fluoride (PVDF) to undergo dehydrofluorination. This then can cause slurry- gelling. Slurry- gelation can then result in inconsistent quality and low yield cathode products, which hinders large- scale cathode manufacturing.

[0004] What is needed are solutions to the above problems, and others, in the field to which the instant disclosure pertains. Set forth herein are such solutions and other related disclosures.SUMMARY

[0005] This disclosure provides anti-gelling nickel-based cathode materials with high energy- density-, small particle size, and high nickel content, and methods of making thereof. The processes herein use high-performance carbon black and functionalized stable binder materials, as well as chemical and electro-chemical compatible dispersants that do not substantially react with lithium lanthanum zirconium oxide (LLZO) garnet materials. The dispersants assist in the distribution of carbon and binder materials in the cathode slurry, without causing gelling. The processes herein are low-cost and efficient to reproduce, making it possible to produce cathode materials on a large scale. The resulting cathode formulation is highly- suitable for use in solid- state lithium metal batteries, as it allows for uniform lithium (Li) metal nucleation on the anode side, resulting in high capacity, fast charge times, and improved cycling stability. Additionally, this formulation is designed to prevent the growth of Li dendrites, which can bedangerous and reduce the overall performance of the battery.

[0006] In one embodiment, set forth herein is a cathode slurry including a solvent, wherein the solvent includes N-methyl-2-pyrrolidone(NMP) ; a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized poly vinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode slurry has a viscosity of less than 200 Pascal second (Pa s). In some embodiments, the viscosity is stable. In some embodiments, the viscosity does not change by more than 10% in a twenty -four hour period. In an embodiment, the solvent is selected from NMP. In an embodiment, the solvent is selected from NMP. In an embodiment, the solvent is NMP.

[0007] In a second embodiment, set forth herein is a cathode comprising a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900.000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode is coated on a metal substrate that is at least twenty meters in length; wherein the direct current (DC) resistance of the cathode is from 5 Q-cm to 25 Q-cm and does not vary by more than 50% across the length of the cathode.

[0008] In a third embodiment, set forth herein is a cathode comprising a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode comprises agglomerates of carbon / polymer having a Ds>o of less than 12 pm2in area as measured by scanning electron microscopy (SEM).

[0009] In a fourth embodiment, set forth herein is a process for making a battery cathode, including mixing a cathode slurry' set forth herein; and depositing the cathode slurry on a metal substrate.

[0010] In a fifth embodiment, set forth herein is a process for manufacturing an anode-less battery', including, providing a cathode set forth herein; providing a solid-state electrolyte; plating lithium metal from the cathode on a side of the solid-state electrolyte opposite the side proximate to the cathode.BRIEF DESCRIPTION OF DRAWINGS

[0011] FIG. 1 shows dynamic viscosity' measurements of cathode slurries withnormal binder (diamonds) with comparison to a functionalized binder (dots).

[0012] FIG. 2 shows dynamic viscosity of cathode slurries with dispersant (triangles) with comparison to cathode slurries without dispersant (dots).

[0013] FIG. 3 shows direct current (DC) resistance of a cathode as a function of dispersant concentration.

[0014] FIG. 4 show-s 1C-1C cycling of an electrochemical cell at 45 °C.DETAILED DESCRIPTION

[0015] The instant disclosure provides compositions and processes for preventing or reducing gelation effects that may occur during cathode preparation and manufacture. Certain processes herein use certain carbon black and binder materials, as well as chemical and electro-compatible dispersants, to achieve good carbon and binder distribution in the cathode slurry without causing gelling. This results in consistent cathode quality and high yield in large-scale production.

[0016] The instant disclosure provides compositions and processes for improving lithium (Li) nucleation during the charging ( / .e., plating) of an electrochemical cell or battery’. The processes use small particle size CAMs and well-controlled carbon and binder agglomeration size to ensure uniform Li nucleation on the anode side. This leads to high capacity7, fast charge times, and improved cycling stability7. It also helps prevent growth of Li dendrites.

[0017] The instant disclosure provides compositions and processes for mixing active materials, conductive additives, and binder in an organic solvent to form an electrode slurry. This mixture contributes to the capacity and energy7, electronic conductivity, and mechanical integrity of the positive electrode. The choice of solvent will influence which binders are suitable and if additional additives are needed. The electrode slurry is then, in certain embodiments, coated onto an aluminum foil current collector using a doctor blade or a slot die coater. The coating is dried and compressed to the desired thickness through calendering or pressing. In some processes, herein, the final steps of the process include electrode slitting, punching, packaging, and assembling and inspecting the cells.DEFINITIONS

[0018] When referring to the compositions and methods provided herein, the following terms have the following meanings unless indicated otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. If there is a plurality of definitions for a term herein, those in this section prevail unless stated otherwise.

[0019] As used herein, the term ‘'about,” when qualifying a number, e.g., about 15 % w / w, refers to the number qualified and optionally the numbers included in a range about that qualified number that includes ± 10% of the 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 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.

[0020] As used herein, the phrase “selected from the group consisting of refers to a single member from the group, more than one member from the group, or a combination of members from the group. A member selected from the group consisting of A. B, and C includes, for example, A only, B only, or C only, as well as A and B, A and C, B and C, as well as A, B, and C.

[0021] As used herein, the term “cathode active material” refers to a material which can intercalate lithium ions or react with lithium ions in a reversible manner. Examples include LiMPCL (M=Fe, Ni, Co, Mn); LixTiyOz, wherein x is from 0 to 8, y is from 1 to 12, z is from 1 to 24; LiMmaNiaCh, wherein a is from 0 to 2; a nickel cobalt aluminum oxide; LiNixMnyCozCh, x+y+z=l, 0<x<l, 0<y<l, and 0<z<l; and LiNixCoyAlzCh, wherein x+y+z=l, and 0<x<l, 0<y<l, and 0<z<l. In these formula, x, y, and z are chosen so that the formula is charge neutral.

[0022] As used herein, the term '‘solid-state cathode” refers to a cathode which does not include any liquid-phase electrolytes.

[0023] As used herein, the terms “cathode” and “anode” refer to the electrodes of a batten’. The cathode and anode are often referred to in the relevant field as the positive electrode and negative electrode, respectively. In some usages, cathode is used in place of positive electrode, and anode is used in place of negative electrode. During a charge cycle in a Li-secondary batte ’, Li ions leave the cathode and move through an electrolyte, to the anode. During a charge cycle, electrons leave the cathode and move through an external circuit to the anode. During a discharge cycle in a Li-secondary batten’, Li ions migrate towards the cathode through an electrolyte and from the anode. During a discharge cycle, electrons leave the anode and move through an external circuit to the cathode.

[0024] As used herein, the term “positive electrode” refers to the electrode in a secondary battery towards which positive ions, e.g., Li+, conduct, flow or move during discharge of the battery. As used herein, the term “negative electrode” refers to the electrode in a secondary' batten' from where positive ions, e.g., Li+, flow or move during discharge of the battery'. In a battery comprised of a Li-metal electrode and a conversion chemistry, intercalation chemistry, or combination conversion / intercalation chemistry-including electrode(i.e., cathode active material; e.g., NiFx, LiNixMnyCozCh (NMC), LiNixAlyCozCh (NCA), wherein x+y+z =1; or LnLasAhCozOn). the electrode having the conversion chemistry, intercalation chemistry, or combination conversion / intercalation chemistry material is referred to as the positive electrode.

[0025] In some usages, '‘cathode’’ is used in place of “positive electrode,” and “anode” is used in place of “negative electrode.” When a Li-secondary battery is charged, Li+ions move from the positive electrode (e.g., NiFx. NMC, NCA) towards the negative electrode (e.g., Li-metal). When a Li- secondary battery is discharged, Li1ions move towards the positive electrode and from the negative electrode.

[0026] As used herein, the term “cathode material” refers to the mixture of components that form the positive electrode. Typically, the cathode material comprises at least one cathode active material and at least one binder.

[0027] As used herein, the term '‘solid separator” refers to a Li+ion-conducting material that is substantially insulating to electrons (e.g., the lithium-ion conductivity is at least 103times, and often 106times, greater than the electron conductivity ), and which acts as a physical barrier or spacer between the positive and negative electrodes in an electrochemical cell.

[0028] As used herein, the term “calendering” refers to a process in which metal rolls, typically of hardened steel, are used to exert pressure on a surface (e.g., the surface of a cathode and its current collector) to alter its properties, e.g, to change the porosity of the material or to smooth its surface. In certain embodiments, calendering is accomplished while also heating the electrode as it is calendered. In certain other embodiments, calendering is accomplished while also cooling the electrode as it is calendered.

[0029] As used herein, “binder” refers to a polymer with the capability to increase the adhesion and / or cohesion of material, such as the solids in a green tape. Suitable binders may include, but are not limited to, PVDF, PVDF-HFP. SBR. and ethylene alpha-olefin copolymer. A '‘binder” refers to a material that assists in the adhesion of another material. For example, as used herein, polyvinyl bulyral is a binder because it is useful for adhering, e.g., garnet materials. Other binders may include polycarbonates. Other binders may include polyacrylates and polymethacrylates. These examples of binders are not limiting as to the entire scope of binders contemplated here, but merely serve 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-l-octene (PE-co-PO). polyethylene-co-poly(methylenecyclopentane) (PE-co-PMCP), poly(methyl methacrylate) (and other acrylics), acrylic, polyvinylacetacetal resin, polyvinyl butyral resin, PVB, polyvinyl acetal resin, stereoblock polypropylenes, polypropylene polymethylpentene copolymer, polyethylene oxide (PEO), PEO block copolymers, silicone, and the like. In certain embodiments, including any of the foregoing, the binder is a polymer selected from the group consisting of polyacrylonitrile (PAN), polypropylene, polyethylene, polyethylene oxide (PEO), poly methyl methacrylate (PMMA), polyvinyl chloride (PVC), polyvinyl pyrrolidone (PVP), polyethylene oxide poly(allyl glycidyl ether) PEO-AGE, polyethylene oxide 2-methoxy ethoxy ethyl glycidyl ether (PEO-MEEGE), polyethylene oxide 2-methoxy ethoxy ethyl glycidyl poly(allyl glycidyl ether) (PEO-MEEGE- AGE), polysiloxane, poly vinylidene fluoride (PVDF), polyvinylidene fluoride hexafluoropropylene (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), poly chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), and poly ethyl acrylate (PEA).

[0030] As used herein, the phrase “dso diameter” refers to the median size, in a distribution of sizes, measured by microscopy techniques or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. “D50” includes the characteristic dimension at which 50% of the particles are smaller than the recited size.

[0031] As used herein, the phrase "doo diameter” refers to a size, in a distribution of sizes, measured by microscopy techniques or other particle size analysis techniques, such as, but not limited to, scanning electron microscopy or dynamic light scattering. “D90” includes the characteristic dimension at which 90% of the particles are smaller than the recited size.

[0032] As used herein, the phrase ‘'film” or '‘thin film” refers to a thin membrane of less than about 10 mm in thickness and greater than about 0.5 nm in thickness. A thin film is also greater than 5 mm in a lateral dimension. A ‘‘film” or “thin-film” may be produced by a continuous process such as tape-casting, slip casting, or screen-printing.

[0033] As used herein, the phrase “film thickness” refers to the distance, or median measured distance, between the top and bottom faces of a film. As used herein, the top and bottom faces refer to the sides of the film having the largest surface area. As used herein, thickness is measured by cross-sectional scanning electron microscopy.

[0034] As used herein, the term “conductive carbon material,” refers to a carbon or carbon- based material that is useful in a cathode for providing electronic conductivity to thecathode.

[0035] As used herein, the term “functionalized polyvinylidene binder,” refers to a poly vinylidene polymer which is functionalized with functional groups.

[0036] As used herein, the term “kneading.” is a process whereby a cathode composition is squeezed, molded, compressed, by hand or by machine but is distinguished from homogeneous mixing.CATHODE SLURRIES AND DRIED, SOLID-STATE CATHODE COMPOSITIONS

[0037] In an embodiment, set forth herein is a cathode slurry including a solvent selected from N-methyl-2-pyrrolidone; a cathode active material including at least 80% by mole of Nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500.000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched poly amines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode slurry has a viscosity of less than 200 Pascal second (Pa s). In some embodiments, the viscosity is stable. In some embodiments, the viscosity does not change by more than 10% in a twenty-four hour period.

[0038] In another embodiment, set forth herein is a cathode slurry' including a solvent selected from N-methyl-2-pyrrolidone; a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500.000 to 900.000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof.

[0039] In another embodiment, set forth herein is a cathode slurry' including a solvent selected from N-methyl-2-pyrrolidone; a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein a concentration of Li2CO3, Li OH. or a combination thereof, in the cathode slurry' is less than 1000 ppm.

[0040] In another embodiment, set forth herein is a cathode comprising a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500.000 to 900,000g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode is coated on a metal substrate that is at leasttwenty meters in length; wherein the direct current (DC) resistance of the cathode is from 5 Q-cm to 25 Q-cm and does not vary by more than 50% across the length of the cathode. In certain embodiments, the DC resistance of the cathode is 6 Q-cm. In certain embodiments, the DC resistance of the cathode is 7 Q-cm. In certain embodiments, the DC resistance of the cathode is 8 Q-cm. In certain embodiments, the DC resistance of the cathode is 9 Q-cm. In certain embodiments, the DC resistance of the cathode is 10 Q-cm. In certain embodiments, the DC resistance of the cathode is 11 Q-cm. In certain embodiments, the DC resistance of the cathode is 12 Q-cm. In certain embodiments, the DC resistance of the cathode is 13 Q- cm. In certain embodiments, the DC resistance of the cathode is 14 Q-cm. In certain embodiments, the DC resistance of the cathode is 15 Q-cm. In certain embodiments, the DC resistance of the cathode is 16 Q-cm. In certain embodiments, the DC resistance of the cathode is 17 Q-cm. In certain embodiments, the DC resistance of the cathode is 18 Q-cm. In certain embodiments, the DC resistance of the cathode is 19 Q-cm. In certain embodiments, the DC resistance of the cathode is 20 Q-cm. In certain embodiments, the DC resistance of the cathode is 21 Q-cm. In certain embodiments, the DC resistance of the cathode is 22 Q- cm. In certain embodiments, the DC resistance of the cathode is 23 Q-cm. In certain embodiments, the DC resistance of the cathode is 24 Q-cm. In certain embodiments, the DC resistance of the cathode is 25 Q-cm.

[0041] In another embodiment, set forth herein is a cathode comprising a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500.000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode comprises agglomerates of conductive carbon material / polymer having a D90 of less than 20 pm2in area as measured by scanning electron microscopy (SEM).

[0042] In another embodiment, set forth herein is a cathode comprising a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode comprises agglomerates of conductive carbon material / polymer having a D90 of less than 12 pm2in area as measured by scanning electron microscopy (SEM).

[0043] In another embodiment, set forth herein is a cathode comprising a cathodeactive material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode comprises agglomerates of conductive carbon material / polymer having a D90 of less than 5 pm2in area as measured by scanning electron microscopy (SEM).

[0044] In certain embodiments, including any of the foregoing, the functionalized poly vinylidene binder has a molecular weight of greater than about 1,200.000 g / mol. In certain embodiments, including any of the foregoing, the functionalized polyvinylidene binder has a molecular weight from about 500,000 to about 1,200,000 g / mol. In certain embodiments, including any of the foregoing, the functionalized poly vinylidene binder has a molecular weight from about 500,000 to about 1,000,000 g / mol. In certain embodiments, including any of the foregoing, the functionalized polyvinylidene binder has a molecular weight from about 500,000 to about 900,000 g / mol. In certain embodiments, including any of the foregoing, the functionalized polyvinylidene binder has a molecular weight from about 500,000 to 600,000 g / mol. In other embodiments, the functionalized polyvinylidene binder has a molecular weight from about 500.000 to 700,000 g / mol. In yet other embodiments, the functionalized polyvinylidene binder has a molecular weight from about 600,000 to 700,000 g / mol. In some other embodiments, the functionalized polyvinylidene binder has a molecular weight from about 600,000 to 800,000 g / mol. In some other embodiments, the functionalized polyvinylidene binder has a molecular weight from about 600,000 to about 900,000 g / mol.

[0045] In some embodiments, including any of the foregoing, set forth herein is a cathode including a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the cathode is coated on a metal substrate that is at least twenty meters in length; wherein the direct current (DC) resistance of the cathode is from 10 £2-cm to 15 Q-cm and does not vary by more than 50% across the length of the cathode.

[0046] In some embodiments, including any of the foregoing, set forth herein is a cathode including a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecularweight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein a concentration of Li2CCh, Li OH. or a combination thereof, in the cathode is less than 1000 ppm.

[0047] In some embodiments, including any of the foregoing, set forth herein is a cathode including a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the moisture content of the cathode is less than about 50 ppm. In some embodiments, including any of the foregoing, the moisture content is measured by Karl Fischer titration.

[0048] In some embodiments, including any of the foregoing, set forth herein is a cathode including a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the moisture content of the cathode is less than about 15 ppm. In some embodiments, including any of the foregoing, the moisture content is measured by Karl Fischer titration.

[0049] In some embodiments, including any of the foregoing, set forth herein is a cathode including a cathode active material including at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), a copolymer of polyacrylonitrile (PAN), and a combination thereof; wherein the peel strength is less than about 10 pound-force per square inch (Ibf / in). In some embodiments, including any of the foregoing, the peel strength is greater than 0 and less than about 5 Ibf / in. In some embodiments, including any of the foregoing, the peel strength is about 1 to about 4 Ibf / in. In some embodiments, including any of the foregoing, the peel strength is measured at an angle of 180° and a speed of 300 mm / min. In some embodiments, including any of the foregoing, the peel strength is measured with an Imada peel tester.

[0050] In some embodiments, including any of the foregoing, the active material is selected from a nickel oxide, a lithium-nickel complex oxide (e.g. , LixNiCh, wherein x is from 1 to 3), a lithium cobalt nickel oxide (LiNii yCoyCh) wherein y is from 0 to 0.2, a spinel-phaselithium-manganese-nickel complex oxide (e.g , LixMm-sNisCh) wherein x is from 1 to 3, wherein s is from 1 to 0.8, or LiNiPCh. or combinations thereof

[0051] In some embodiments, including any of the foregoing, the cathode active material is selected from LiMPCh (M=Fe, Ni, Co, Mn); LixTiyOz, wherein x is from 0 to 8, y is from 1 to 12, z is from 1 to 24; LiMnzaNiaCh, wherein a is from 0 to 2; a nickel cobalt aluminum oxide; LiNixMnyCozCh, x+y+z=l, 0.8<x<l, 0<y<l, and 0<z<l; and LiNixCoyAlzCh, wherein x+y+z=l, and 0.8<x<l, 0<y<l, and 0<z<l.

[0052] In some other embodiments, the cathode active material is, or includes, a manganese oxide (MnO), iron oxides, copper oxides, nickel oxides, lithium-manganese complex oxides (e.g. , LixMmCh or LixMnCh), lithium-nickel complex oxides (e.g. , LixNiCh), lithium-cobalt complex oxides (e.g. LixCoCh), lithium cobalt nickel oxides (LiNii-yCoyCh), lithium-manganese- cobalt complex oxides (e.g.. LiMnyCoi-yCh), spinel -phase lithium- manganese-nickel complex oxides (e.g, LixMrm-yNiyC ), lithium phosphates having an olivine structure (e.g., LixFePCh, LixFeiyMnyPO4, LixCoPCh), lithium phosphates having a NASICON-type structure (e.g., Li?V2(PO4)3), iron (III) sulfate (Fe2(SO4)3), and vanadium oxides (e.g.. V2O5). In some embodiments, x and y in these chemical formulas he within the ranges of l<x<5. and 0<y<l. In some embodiments, the cathode active material is LiCoCh. LixV2(PO4)s, LiNiPCh, and LiFePCh. In some embodiments, the cathode active material is doped LiCoCh, including La-doped LiCoCh and Al-doped LiCoCh.

[0053] In some embodiments, including any of the foregoing, the cathode active material is LiNixMnyCozCh. x+y+z=l, 0.8<x<l, 0<y<l, and 0<z<l and wherein x+y+z=l.

[0054] In some embodiments, including any of the foregoing, the cathode active material is LiNixMnyCozCh and either (a)-(e):(a) x is 0.8. y is 0.1, and z is 0.1;(b) 0.8<x<0.97, 0<y<0.2, and 0<z<0.2;(c) 0.8<x<0.90, 0<y<0.2, and 0<z<0.2;(d) 0.8<x<0.85, 0<y<0.2, and 0<z<0.2; or(e) 0.8<x<0.83, 0<y<0.2, and0<z<0.2. In the above formula, x, y, and z sum to 1.

[0055] In some embodiments, including any of the foregoing, the conductive carbon material is selected from carbon black (e.g, conductive carbon black C65, C45), activated carbon, , vapor grown carbon fiber (VGCF), carbon fibers, carbon nanotubes, or a combination thereof.

[0056] In some embodiments, including any of the foregoing, the total solid contentis from about 65 to 70% by volume. In some embodiments, including any of the foregoing, the total solid content is from about 66.5 to 68% by volume.

[0057] In some embodiments, including any of the foregoing, the porosity is 40 % to 60 % by volume. In some embodiments, including any of the foregoing, the porosity is 45 % to 55 % by volume. In some embodiments, including any of the foregoing, the porosity is 45 % to 50 % by volume. In some embodiments, including any of the foregoing, the porosity7is 50 % to 60 % by volume.

[0058]

[0059] In some embodiments, including any of the foregoing, the amount of H2O is less than 1,000 ppm. In some embodiments, including any of the foregoing, the amount of H2O is less than 750 ppm. In some embodiments, including any of the foregoing, the amount of H2O is less than 500 ppm.

[0060] In some embodiments, including any of the foregoing, the amount of conductive carbon material is 0.1 % by weight to 10 % by weight. In some embodiments, including any of the foregoing, the amount of conductive carbon material is 0.1 % by weight to 8 % by weight. In some embodiments, including any of the foregoing, the amount of conductive carbon material is 0.1 % by weight to 5 % by weight.

[0061] In some embodiments, including any of the foregoing, the amount of Li2CC>3 and LiOH is less than 500 ppm. In some embodiments, including any of the foregoing, the amount of Li2COs and LiOH is less than 400 ppm. In some embodiments, including any of the foregoing, the amount of Li2COs and LiOH is less than 300 ppm.

[0062] In some embodiments, including any of the foregoing, the concentration of Li2COs is less than 400 ppm. In some embodiments, including any of the foregoing, the concentration of Li2CO3 is less than 300 ppm. In some embodiments, including any of the foregoing, the concentration of Li2CCh is less than 200 ppm.

[0063] In some embodiments, including any of the foregoing, the amount of Li2CO3 and LiOH is less than 400 ppm. I.n some embodiments, including any of the foregoing, the amount of Li2COs and LiOH is less than 300 ppm. In some embodiments, including any of the foregoing, the amount of Li2COs and LiOH is less than 200 ppm

[0064] In some embodiments, including any of the foregoing, the thickness of the cathode is about 100 to about 350 pm. In some embodiments, including any of the foregoing, the thickness of the cathode is about 100 to about 325 pm. In some embodiments, including any of the foregoing, the thickness of the cathode is about 100 to 300 pm.

[0065] In some embodiments, including any of the foregoing, the amount of dispersantis

[0066] 0.01 % to 3 % by weight. In some embodiments, including any of the foregoing, the amount of dispersant is 0. 1 % to 3 % by weight. In some embodiments, including any of the foregoing, the amount of dispersant is 1 % to 3 % by weight.

[0067] In some embodiments, including any of the foregoing, the amount of dispersant is 0.1 % to 0.8 % by weight.

[0068] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has a mono-modal particle size.

[0069] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has a D90 particle size of 1 to 10 microns (pm).

[0070] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has a D90 particle size of about 4 microns.

[0071] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has a D90 particle size of about 3.8 pm.

[0072] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has a D90 particle size of about 3.2 pm.

[0073] In some embodiments, including any of the foregoing, the functionalized poly vinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol is functionalized with functional groups.

[0074] In some embodiments, including any of the foregoing, an agglomeration size is as small as possible, and it is strictly controlled and measured by SEM, uCT and radiograph.

[0075] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes less than 5% by mole of a dopant. In certain examples, the dopant is aluminum (Al).

[0076] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes less than 5% by mole of Al. In certain embodiments, the cathode active material including at least 80% by mole of Ni includes less than 4% by mole of Al. In certain embodiments, the cathode active material including at least 80% by mole of Ni includes less than 3% by mole of Al. In certain embodiments, the cathode active material including at least 80% by mole of Ni includes less than 2% by mole of Al. In certain embodiments, the cathode active material including at least 80% by mole of Ni includes less than 1% by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.01 % bymole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.02 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.03 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.04 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.05 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.2 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.3 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.4 % by mole of Al. In certain embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni includes at least 0.5 % by mole of Al.

[0077] In some embodiments, including any of the foregoing, the cathode active material including at least 80% by mole of Ni has less than a 10 nm thin surface coating layer. In some examples, the coating is a lithium phosphate. In some examples, the coating is a lithium zirconium phosphate. In some examples, the coating is a lithium zirconium oxide. In certain embodiments, the thin surface coating is 10 nm in thickness. In certain embodiments, the thin surface coating is 9 nm in thickness. In certain embodiments, the thin surface coating is 8 nm in thickness. In certain embodiments, the thin surface coating is 7 nm in thickness. In certain embodiments, the thin surface coating is 6 nm in thickness. In certain embodiments, the thin surface coating is 5 nm in thickness. In certain embodiments, the thin surface coating is 4 nm in thickness. In certain embodiments, the thin surface coating is 3 nm in thickness. In certain embodiments, the thin surface coating is 2 nm in thickness. In certain embodiments, the thin surface coating is 1 nm in thickness.

[0078] In some embodiments, including any of the foregoing, the mass loading of the cathode active material including at least 80% by mole of Ni is 20 mg / cm2to 40 mg / cm2In some embodiments, including any of the foregoing, the mass loading of the cathode active material including at least 80% by mole of Ni is 20 mg / cm2to 30 mg / cm2. In some embodiments, including any of the foregoing, the mass loading of the cathode active material including at least 80% by mole of Ni is 30 mg / cm2to 40 mg / cm2. In some embodiments, including any of the foregoing, the mass loading of the cathode active material including at least 80% by mole of Ni is 25 mg / cm2to 35mg / cm2In some embodiments, including any of the foregoing, the mass loading of the cathode active material including at least 80% by mole of Ni is 30 mg / cm2to 35 mg / cm2.

[0079] In some embodiments, including any of the foregoing, the cathode includes 91 % - 99 % by weight cathode active material including at least 80% Ni.

[0080] In some embodiments, including any of the foregoing, the cathode includes 91% by weight NMC; 5% by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; 4% by weight conductive carbon material; and having 41% by volume porosity; and 20 mg / cm2loading of cathode active material including at least 80% Ni.

[0081] In some embodiments, including any of the foregoing, the cathode includes: 95% by weight NMC; 2.3% by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; 2.7 % by weight conductive carbon material; and having 25 % by volume porosity; and 29 mg / cm2loading of cathode active material including at least 80% Ni.

[0082] In some embodiments, including any of the foregoing, the cathode includes: 95% by weight NMC; 2% by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; 3% by weight conductive carbon material; and having 41 % by volume porosity; and 20 mg / cm2loading of cathode active material including at least 80% Ni.

[0083] In some embodiments, including any of the foregoing, the cathode includes 95 % by weight cathode active material including at least 80% Ni; 2 % by weight conductive carbon material; 3 % by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; and 0.1 % by weight dispersant.

[0084] In some embodiments, including any of the foregoing, the cathode includes 95 % by weight cathode active material including at least 80% Ni; 2.3 % by weight conductive carbon material; 2.7 % by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; and 0.1 % by weight dispersant.

[0085] In some embodiments, including any of the foregoing, the active material is bead- milled.

[0086] In some embodiments, including any of the foregoing, the active material is not bead- milled.

[0087] In some embodiments, including any of the foregoing, set forth herein is solid-state cathode including a cathode composition set forth herein.

[0088] In some embodiments, including any of the foregoing, set forth herein is adried form of the cathode slurry set forth herein.PROCESSES FOR MAKING CATHODE SLURRIES AND DRIED, SOLID-STATE CATHODE COMPOSITIONS

[0089] In some embodiments, including any of the foregoing, set forth herein is a process for making a battery cathode, including mixing a cathode slurry set forth herein; and depositing the cathode slurry on a metal substrate.

[0090] In some embodiments, including any of the foregoing, the mixing does not include kneading.

[0091] In some embodiments, including any of the foregoing, the process includes dry ing the cathode slurry.

[0092] In some embodiments, including any of the foregoing, the process includes compressing the cathode slurry.

[0093] In some embodiments, including any of the foregoing, the process includes calendering the cathode slurry .

[0094] In some embodiments, including any of the foregoing, the process includes slitting the metal substrate having the cathode slurry thereupon.

[0095] In some embodiments, including any of the foregoing, the process includes punching the metal substrate having the cathode slurry7thereupon.

[0096] In some embodiments, including any of the foregoing, the process includes assembling the cathode slurry into a battery cell.

[0097] In some embodiments, including any of the foregoing, set forth herein is a process for manufacturing an anode-less battery, including, providing a cathode set forth herein; providing a solid-state electrolyte; plating lithium metal from the cathode on a side of the solid-state electrolyte opposite the side proximate to the cathode. In some embodiments, the solid-state electrolyte is a lithium-stuffed garnet solid-state electrolyte.

[0098] NON-LIMITING EMBODIMENTS

[0099] The present disclosure provides at least the following non-limiting embodiments:(a) A cathode slurry comprising: a solvent comprising N-methyl-2 -pyrrolidone; a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of hyperbranched polyamines(HBPA), a polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode slurry has a viscosity of less than 200 Pascal second (Pa s).(b) A cathode comprising: a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode is coated on a metal substrate that is at least twenty meters in length; wherein the direct current (DC) resistance of the cathode is from 5 Q-cm to 25 Q-cm and does not vary by more than 50% across the length of the cathode.(c) The cathode of (b), wherein the wherein the cathode is coated on a metal substrate that is at least one-hundred meters in length.(d) The cathode of (b) or (c), wherein the wherein the cathode is coated on a metal substrate that is at least one-thousand meters in length.(e) A cathode comprising: a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched poly amines (HBPA), polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode comprises agglomerates of carbon / polymer having a D$>o of less than 20 pm2in area as measured by scanning electron microscopy (SEM).(f) The cathode of (e), wherein the cathode comprises agglomerates of carbon / polymer having a D90 of less than 12 pm2in area as measured by scanning electron microscopy (SEM).(g) The cathode slurry or cathode of any one of embodiments (a)-(f), wherein theactive material is selected from a nickel oxide, a lithium-nickel complex oxide (e.g, LixNiCh, wherein x is from 1 to 3), a lithium cobalt nickel oxide (LiNii-yCoyCh) wherein y is from 0 to 0.2, a spinel-phase lithium- manganesenickel complex oxide (e.g., LixMm-sNisC ) wherein s is from 1 to 0.8, or L1N1PO4.(h) The cathode slurry or cathode of any one of embodiments (a)-(g), wherein the cathode active material is selected from LiMPCh (M=Fe, Ni, Co, Mn); LixTiyOz, wherein x is from 0 to 8, y is from 1 to 12, z is from 1 to 24; LiMn2aNiaO4, wherein a is from 0 to 2; a nickel cobalt aluminum oxide; LiNixMnyCozCh, x+y+z=l, 0.8<x<l, 0<y<l, and 0<z<l; and LiNixCoyAlzCh, wherein x+y+z=l, and 0.8<x<l, 0<y<l, and 0<z<l.(i) The cathode slurry- or cathode of any one of embodiments (a)-(h), wherein the cathode active material is LiNixMnyCozCh, x+y+z=l. 0.8<x<l, 0<y<l, and 0<z<l and wherein x+y+z=l.(j) The cathode slum7or cathode of any one of embodiments (a)-(i), wherein the cathode active material is LiNixMnyCozCh and either: x is 0.8, y is 0.1. and z is 0.1; 0.8<x<0.97. 0<y<0.2. and 0<z<0.2;0.8<x<0.90, 0<y<0.2, and 0<z<0.2;0.8<x<0.85, 0<y<0.2, and 0<z<0.2; or0.8<x<0.83, 0<y<0.2, and 0<z<0.2.(k) The cathode slurry or cathode of any one of embodiments (a)-(j), wherein the conductive carbon material is selected from carbon black, activated carbon, C65, C45, VGCF, carbon fibers, carbon nanotubes, or a combination thereof.(l) The cathode slurry or cathode of any one of embodiments (a)-(k), wherein the total solid content is from about 66.5 to 68% by volume.(m) The cathode slurry of any one of embodiments (a)-(l), wherein the porosity is 40 to 60 % by volume.(n) The cathode si urn- of any one of embodiments (a)-(m), wherein the porosity- is 45 to 50 % by volume.(0) The cathode slurry of any one of embodiments (a)-(n), wherein the amount of H2O is less than 1,000 ppm.(p) The cathode slurry or cathode of any one of embodiments (a)-(o), wherein the amount of carbon material is 0. 1 % by w eight to 10 % by w eight.(q) The cathode slurry or cathode of any one of embodiments (a)-(p), wherein the amount of Li2CCh and Li OH is less than 500 ppm.(r) The cathode slurry or cathode of any one of embodiments (a)-(q), wherein the concentration of Li2COs is less than 400 ppm.(s) The cathode slurry' or cathode of any one of embodiments (a)-(r), wherein the amount of Li2CO3 and Li OH is less than 400 ppm.(t) The cathode slurry or cathode of any one of embodiments (a)-(s), wherein the thickness of the cathode is about 100 to 300 pm.(u) The cathode slurry' or cathode of any one of embodiments (a)-(t), wherein the amount of dispersant is 0.01 % to 3 % by weight.(v) The cathode slurry or cathode of any one of embodiments (a)-(u), wherein the amount of dispersant is 0. 1 % to 0.8 % by' weight.(w) The cathode slurry' or cathode of any one of embodiments (a)-(v), wherein the cathode active material comprising at least 80% by mole of Ni has a mono- modal particle size.(x) The cathode slurry' or cathode of any one of embodiments (a)-(w), wherein the cathode active material comprising at least 80% by mole of Ni has a D90 particle size of 1 pm to 10 pm.(y) The cathode slurry or cathode of any one of embodiments (a)-(x), wherein the cathode active material comprising at least 80% by mole of Ni has a D90 particle size of about 4 pm.(z) The cathode slurry' or cathode of any one of embodiments (a)-(y), wherein the cathode active material comprising at least 80% by mole of Ni has a D90 particle size of about 3.8 pm.(aa) The cathode slurry' or cathode of any one of embodiments (a)-(z), wherein the cathode active material comprising at least 80% by mole of Ni has a D90 particle size of about 3.2 pm.(bb) The cathode slurry' or cathode of any one of embodiments (a)-(aa), w herein the functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol is functionalized with functional groups.(cc) The cathode slurry’ or cathode of any one of embodiments (a)-(bb), wherein the functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol is functionalized with carbonyl groups.(dd) The cathode slurry' or cathode of any one of embodiments (a)-(cc), wherein an agglomeration size is as small as possible, and it is strictly controlled and measured by SEM, uCT and radiograph.(ee) The cathode slurry' or cathode of any one of embodiments (a)-(dd), wherein thecathode active material comprising at least 80% by mole of Ni comprises less than 5% by mole of a dopant.(ff) The cathode slurry or cathode of any one of embodiments (a)-(ee), wherein the cathode active material comprising at least 80% by mole of Ni has less than a 10 nm thin surface coating layer.(gg) The cathode slurry or cathode of any one of embodiments (a)-(ff), wherein the mass loading of the cathode active material comprising at least 80% by mole of Ni is 20 mg / cm2to 30 mg / cm2(hh) The cathode slurry or cathode of any one of embodiments (a)-(gg). comprising 91 % - 99 % by weight cathode active material comprising at least 80% by mole ofNi.(ii) The cathode slurry or cathode of any one of embodiments (a)-(hh), comprising: 91% by weight NMC;5% by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol;4% by weight carbon material; and having 41% by volume porosity; and20 mg / cm2loading of cathode active material comprising at least 80% by mole of Ni.(jj) The cathode slurry or cathode of any one of embodiments (a)-(hh), comprising: 95% by weight NMC;2.3% by weight functionalized polyvinylidene binder having a molecular weight of from about 500.000 to 900,000 g / mol;2.7 % by weight carbon material; and having 25 % by volume porosity; and29 mg / cm2loading of cathode active material comprising at least 80% by mole of Ni.(kk) The cathode slurry or cathode of any one of embodiments (a)-(hh), comprising: 95% by weight NMC;2% by weight functionalized polyvinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol;3% by weight carbon material; and having 41% by volume porosity; and20 mg / cm2loading of cathode active material comprising at least 80% by mole of Ni.(11) The cathode slurry’ or cathode of any one of embodiments (a)-(hh), comprising 95 % by weight cathode active material comprising at least 80% by mole of Ni;2 % by weight carbon material;3 % by weight functionalized poly vinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; and% by weight dispersant.(mm) The cathode slurry or cathode of any one of embodiments (a)-(hh), comprising:95 % by weight cathode active material comprising at least 80% by mole of Ni;2.3 % by weight carbon material;2.7 % by weight functionalized poly vinylidene binder having a molecular weight of from about 500,000 to 900,000 g / mol; and% by weight dispersant.(nn) The cathode slum or cathode of any one of embodiments (a)-(mm), wherein the active material is bead-milled.(oo) The cathode slurry' or cathode of any one of embodiments (a)-(nn), wherein the active material is not bead-milled.(pp) The cathode slurry or cathode of any one of embodiments (a)-(oo), wherein a concentration of Li2COs, LiOH, or a combination thereof, in the cathode is less than 1000 ppm(qq) The cathode slurry’ or cathode of any one of embodiments (a)-(pp), wherein the dispersant is present at 0. 1-0.3 wt%.(rr) A solid-state cathode comprising the cathode of any one of embodiments (b)- (qq)-(ss) A dried form of the cathode slurry of any one of embodiments (a)-(qq).(tt) A process for making a battery cathode, comprising mixing the cathode slurry of any one of embodiments (a)-(qq); and depositing the cathode slurry' on a metal substrate.(uu) The process of (tt), where the mixing does not comprise kneading.(vv) The process of (tt) or (uu). comprising drying the cathode slurry.(ww) The process of any one of embodiments (tt)-(vv), comprising compressing the cathode slurry.(xx) The process of any one of embodiments (tt)-(ww), comprising calendering the cathode slurry.(yy) The process of any one of embodiments (tt)-(xx), comprising slitting the metal substrate having the cathode slurry thereupon.(zz) The process of any one of embodiments (tt)-(yy), comprising punching the metal substrate having the cathode slurry' thereupon.(aaa) The process of any one of embodiments (tt)-(zz), comprising assembling thecathode slurry into a battery cell.(bbb) A process for manufacturing an anode-less battery', comprising, providing a cathode of any one of embodiments (a)-(qq); providing a solid-state electrolyte; plating lithium metal from the cathode on a side of the solid-state electrolyte opposite the side proximate to the cathode.EXAMPLES

[0100] As used herein, the symbols and conventions used in these processes, schemes and examples, regardless of whether a particular abbreviation is specifically defined, are consistent with those used in the contemporary scientific literature.PROPHETIC EXAMPLE - EXAMPLE 1 - GENERAL PREPARATION OF CATHODE AND CURRENT COLLECTOR

[0101] For the preparation of an exemplary high-energy-density cathode / current collector useful in the present invention, a cathode would be casted on aluminum foil (e.g.. Armor) that would be 100 mm long by 260 mm wide by 18 pm thick.

[0102] A slurry' would be prepared that includes the solids (a) 95-99% w / w active material (e.g., a high nickel-content NMC). (b) 0.5-3% w / w binder (e.g.. Kureha9700); (c) 0.5- 3% w / w carbon (e.g.. C65); and (d) a 0.01-3.01% surfactant (e.g.. a hyperbranched polyamine copolymer, such as BYK2205, or a polyacrylonitrile copolymer, such as Zeon BM-740H), in which the sum of a + b + c + d is 100%. The solvent would be NMP. The final slurry solid content would be about 65 % to 70 % by weight. Herein, high nickel-content means at least 80% by mole of nickel, such as LiNio sMno.iCoo.i.

[0103] The slurry would be mixed via multiple step process and casted using a die coating system by the roll-to-roll casting method and using a doctor's blade casting. The target loading would be about 29 mg / cm2The initial thickness of the electrode after slurry casting would be between about 245 pm to about 280 pm.

[0104] After coating, the electrode would be dried by a multiple stage drying process. The temperatures of the stages were 80 °C, 100 °C. and 110 °C, and the cathode would be passed through the stages at the speed of 1 m / min. The electrode would be held for 8 hours at 110 °C. After the stages, the entire roll would be dried again in oven for 8 hours at 110 °C under N2 purging.

[0105] After dry ing, the electrode would be calendered (e.g. , using an ONO calendaring tool from the initial thickness to the final thickness of about 180 to 200 pm, based on the need of final porosity %.

[0106] EXAMPLE 2 - CYCLING DATA

[0107] Cells were constructed using a lithium-stuffed garnet separator and a high nickel-content NMC containing cathode. Before cell assembly, the cathode electrode was soaked in a catholyte. After soaking, excess catholyte was removed by dabbing. An anode current collector foil with a tab was placed in contact with the anode side of the separator and a cathode current collector foil with a tab was placed in contact with the Al foil on the back of the cathode electrode. A pouch was sealed around the cell, with the tabs sticking out of the cell to make electrical connections to each electrode.

[0108] The cells were cycled at 1C-1C at 45 °C. The results are shown in FIG. 4. As seen in FIG. 4, the cells constructed with cathodes including dispersant demonstrate a capacity retention of above 90 % for up to 425 cycles. In contrast, the cells constructed with cathodes that did not include dispersant exhibit a sharp drop off in capacity' retention starting at 125 cycles that reduces to below 40 % at 425 cycles.

[0109] The embodiments and examples described above are intended to be merely illustrative and non-limiting. Those s killed in the art will recognize or will be able to ascertain using no more than routine experimentation, numerous equivalents of specific compounds, materials and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims.

[0110] All publications and patent, applications cited in this specification are herein incorporated by reference as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. While the claimed subject matter has been described in terms of various embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the subject matter limited solely by the scope of the following claims, including equivalents thereof.

Claims

CLAIMSWhat is claimed:

1. A cathode slurry comprising: a solvent comprising N-methyl-2-pyrrolidone; a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of hyperbranched polyamines (HBPA), a polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode slurry has a viscosity of less than 200 Pascal second (Pa s).

2. A cathode comprising: a cathode active material comprising at least 80% by mole of nickel (Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode is coated on a metal substrate that is at least twenty meters in length; wherein the direct current (DC) resistance of the cathode is from 5 Q-cm to25 Q-cm and does not vary by more than 50% across a length of the cathode.

3. The cathode of claim 2, wherein the cathode is coated on a metal substrate that is at least one-hundred meters in length.

4. The cathode of claim 2 or 3, wherein the cathode is coated on a metal substratethat is at least one-thousand meters in length.

5. A cathode comprising: a cathode active material comprising at least 80% by mole of nickel(Ni); a conductive carbon material; a functionalized polyvinylidene binder having a molecular weight from about 500,000 to 900,000 g / mol; and a dispersant selected from the group consisting of a copolymer of hyperbranched polyamines (HBPA), polyacrylonitrile (PAN), copolymers thereof, and combinations thereof; wherein the cathode comprises agglomerates of carbon / polymer having a D90 of less than 20 pm2in area as measured by scanning electron microscopy (SEM).

6. The cathode of claim 5, wherein the cathode comprises agglomerates of carbon / polymer having a D90 of less than 12 pm2in area as measured by scanning electron microscopy (SEM).

7. The cathode slurry or cathode of any one of claims 1-6, wherein the cathode active material is selected from a nickel oxide, a lithium-nickel complex oxide comprising LixNiCh, wherein x is from 1 to 3; a lithium cobalt nickel oxide comprising LiNii-yCoyCh, wherein y is from 0 to 0.2; a spinel-phase lithium- manganese-nickel complex oxide comprising LixM -sNisCh, wherein x is from 1 to 3, s is from 1 to 0.8; or LiNiPCri.

8. The cathode slurry or cathode of any one of claims 1-7, wherein the cathode active material is selected from LiMPCri (M=Fe, Ni, Co, Mn); LixTiyOz, wherein x is from 0 to 8, y is from 1 to 12, z is from 1 to 24; LiMmaNiaCh, wherein a is from 0 to 2; a nickel cobalt aluminum oxide; LiNixMnyCozC>2, x+y+z=l, 0.8<x<l, 0<y<l, and 0<z<l; or LiNixCoyAlzCh, wherein x+y+z=l, and 0.8<x<l, 0<y<l, and 0<z<l.

9. The cathode slurry or cathode of any one of claims 1-8, wherein the cathode active material is LiNixMnyCozCh, x+y+z=l, 0.8<x<l, 0<y<l, and 0<z<l, and wherein x+y+z= 1.

10. The cathode slurry or cathode of any one of claims 1-9, wherein the cathode active material is LiNixMnyCozCh and either:x is 0.8, y is 0.1, and z is 0.1;0.8<x<0.97, 0<y<0.2, and 0<z<0.2;0.8<x<0.90, 0<y<0.2, and 0<z<0.2;0.8<x<0.85, 0<y<0.2, and 0<z<0.2; or0.8<x<0.83, 0<y<0.2, and 0<z<0.2.

11. The cathode slurry or cathode of any one of claims 1-10, wherein the conductive carbon material is selected from carbon black, activated carbon, vapor grown carbon fiber (VGCF), carbon fibers, carbon nanotubes, or a combination thereof.

12. The cathode slurry or cathode of any one of claims 1-11, wherein the total solid content is from about 66.5 to 68% by volume.

13. The cathode slurry of any one of claims 1-12, wherein the porosity is 40 to 60 % by volume.

14. The cathode slurry of any one of claims 1-13, wherein the porosity is 45 to 50 % by volume.

15. The cathode slurry of any one of claims 1-14, wherein the amount of H2O is less than 1,000 ppm.

16. The cathode slurry or cathode of any one of claims 1-15, wherein the amount of carbon material is 0. 1 % by weight to 10 % by weight.

17. The cathode slurry or cathode of any one of claims 1-16, wherein the cathode active material includes Li2CO3 and LiOH, wherein the amount of Li2CO3 and LiOH is less than 500 ppm.

18. The cathode slurry or cathode of any one of claim 17, wherein the concentration of Li2CC>3 is less than 400 ppm.

19. The cathode slurry or cathode of any one of claim 17, wherein the amount of Li2CO3 and LiOH is less than 400 ppm.

20. The cathode of any one of claims 2-19, wherein the thickness of the cathode is about 100 to 300 pm.

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