# US 2019/0173079 A1 · Method of Producing Participate Electrode Materials for Alkali Metal Batteries > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0173079 A1 - Document ID: US20190173079A1 - Status: Published application - Kind: A1 - Application number: 15/860,176 - Filed: 2018-01-02 - Published: 2019-06-06 - Earliest claimed: 2017-12-05 - Assignees: Nanotek Instruments, Inc. - Applicants: Nanotek Instruments, Inc. - Inventors: Aruna Zhamu; Hui He; Baofei Pan; Bor Z. Jang - Web page: https://patentgrep.com/patent/US20190173079A1 ## CPC - H01M 4/364: {as mixtures} - H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof - H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx - H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - H01M 4/134: Electrodes based on metals, Si or alloys - H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy - H01M 4/139: Processes of manufacture - H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx - H01M 4/1393: of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - H01M 4/1395: of electrodes based on metals, Si or alloys - H01M 4/1397: of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy - H01M 4/386: {Silicon or alloys based on silicon} - H01M 4/483: {for non-aqueous cells (H01M4/485 takes precedence)} - H01M 4/502: {for non-aqueous cells (H01M4/505 takes precedence)} - H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy - H01M 4/523: {for non-aqueous cells (H01M4/525 takes precedence)} - H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy - H01M 4/581: {Chalcogenides or intercalation compounds thereof} - H01M 4/5815: {Sulfides} - H01M 4/582: {Halogenides} - H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines} - H01M 4/587: for inserting or intercalating light metals - H01M 4/60: of organic compounds - H01M 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers - H01M 4/622: {being polymers} - H01M 4/625: {Carbon or graphite} - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium - H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type - H01M 10/0569: characterised by the solvents - H01M 2300/0037: Mixture of solvents - H01M 2300/0085: Immobilising or gelification of electrolyte - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract Provided is method of producing anode or cathode particulates for an alkali metal battery. The method comprises: (a) preparing a slurry containing particles of an anode or cathode active material, an electron-conducting material, and a lithium or sodium salt and an optional polymer dissolved in a volatile liquid medium; and (b) conducting a particulate-forming means to convert the slurry into multiple anode or cathode particulates, wherein an anode or a cathode particulate is composed of (i) particles of the active material, (ii) the electron-conducting material, and (iii) lithium or sodium salt, the optional polymer, and the volatile liquid medium, wherein the electron-conducting material forms a 3D network of electron-conducting pathways wherein the anode or cathode particulate has an electrical conductivity from about 10−7 S/cm to 300 S/cm; and (c) partially or completely removing the volatile liquid medium from the multiple anode particulates or cathode ## Claims ### Claim 1 A method of producing anode particulates or cathode particulates for use in an alkali metal battery, said method comprising: a) preparing a slurry containing particles of an anode active material or cathode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, an electron-conducting material, and a lithium salt or sodium salt and an optional polymer dissolved in a volatile liquid medium, which is different in composition than a liquid solvent of an intended electrolyte for said battery; b) conducting a particulate-forming means to convert said slurry into multiple anode particulates or cathode particulates having a dimension from 10 nm to 300 μm, wherein an anode particulate or a cathode particulate is composed of (i) particles of said anode or cathode active material, (ii) said electron-conducting material, and (iii) said lithium salt or sodium salt, said optional polymer, and said volatile liquid medium, wherein said electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with said anode active material or cathode active material and said lithium salt or sodium salt is in ionic contact with said anode or cathode active material and wherein said anode particulate or cathode particulate has an electrical conductivity from about 10−7 S/cm to about 300 S/cm; and c) partially or completely removing said volatile liquid medium from said multiple anode particulates or cathode particulates. ### Claim 2 (depends on 1) The method of claim 1, wherein said particulate-forming means is selected from pan-coating method, air-suspension coating method, centrifugal extrusion, vibration nozzle method, spray-drying, Interfacial polycondensation or interfacial cross-linking, in situ polymerization, matrix polymerization, or a combination thereof. ### Claim 3 (depends on 1) The method of claim 1, wherein said lithium salt is selected from lithium carbonate (Li2CO3), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-Fluoroalkyl-Phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, or a combination thereof. ### Claim 4 (depends on 1) The method of claim 1, wherein said sodium salt is selected from sodium perchlorate (NaClO4), sodium hexafluorophosphate (NaPF6), sodium borofluoride (NaBF4), sodium hexafluoroarsenide, sodium trifluoro-metasulfonate (NaCF3SO3), bis-trifluoromethyl sulfonylimide sodium (NaN(CF3SO2)2), sodium trifluoromethanesulfonimide (NaTFSI), bis-trifluoromethyl sulfonylimide sodium (NaN(CF3SO2)2), or a combination thereof ### Claim 5 (depends on 1) The method of claim 1, wherein said polymer contains a lithium ion-conducting or sodium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated polymer, or a combination thereof. ### Claim 6 (depends on 1) The method of claim 1, wherein said sulfonated polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetrafluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene (PCTFE), sulfonated perfluoroethylene-propylene copolymer (FEP), sulfonated ethylene-chlorotrifluoroethylene copolymer (ECTFE), sulfonated polyvinylidenefluoride (PVDF), sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene (ETFE), sulfonated polybenzimidazole (PBI), sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, a sulfonated bi-cyclic polymer, their chemical derivatives, copolymers, blends and combinations thereof. ### Claim 7 (depends on 1) The method of claim 1, wherein said alkali metal battery is a lithium-ion battery and said anode active material is selected from the group consisting of: (a) particles of natural graphite, artificial graphite, mesocarbon microbeads (MCMB), needle coke, carbon particles, carbon fibers, carbon nanotubes, and carbon nanofibers; (b) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), nickel (Ni), cobalt (Co), manganese (Mn), titanium (Ti), iron (Fe), and cadmium (Cd); (c) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric; (d) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Nb, Mo, Pb, Sb, Bi, Zn, Al, Fe, Ni, Co, Ti, Mn, or Cd, and their mixtures or composites; (e) prelithiated versions thereof; (f) prelithiated graphene sheets; and combinations thereof. ### Claim 8 (depends on 1) The method of claim 1, wherein the alkali metal battery is a sodium-ion battery and said anode active material contains an alkali intercalation compound selected from the following groups of materials: (a) sodium- or potassium-doped silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), and mixtures thereof; (b) sodium- or potassium-containing alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures; (c) sodium- or potassium-containing oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; (d) sodium or potassium salts; and (e) graphene sheets pre-loaded with sodium or potassium. ### Claim 9 (depends on 1) The method of claim 1, wherein said alkali metal battery is a sodium-ion battery and said anode active material contains an alkali intercalation compound selected from petroleum coke, carbon black, amorphous carbon, activated carbon, hard carbon, soft carbon, templated carbon, hollow carbon nanowires, hollow carbon sphere, titanates, NaTi2(PO4)3, Na2Ti3O7, Na2C8H4O4, Na2TP, NaxTiO2 (0.2≤x≤1.0), Na2C8H4O4, carboxylate based materials, C8H4Na2O4, C8H6O4, C8H5NaO4, C8Na2F4O4, C10H2Na4O8, C14H4O6, C14H4Na4O8, or a combination thereof. ### Claim 10 (depends on 1) The method of claim 1, wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnOx, prelithiated SiOx, prelithiated iron oxide, prelithiated VO2, prelithiated Co3O4, prelithiated Ni3O4, prelithiated Mn3O4, or a combination thereof, wherein 1≤x≤2. ### Claim 11 (depends on 1) The method of claim 1, wherein said anode active material is in a form of nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm. ### Claim 12 (depends on 1) The method of claim 1, wherein said anode active material is coated with a layer of carbon, a conducting polymer, or a graphene sheet. ### Claim 13 (depends on 1) The method of claim 1, wherein said conducting material contains an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof. ### Claim 14 (depends on 1) The method of claim 1, wherein said electrolyte has a lithium ion conductivity or sodium ion conductivity from 10−7 S/cm to 0.05 S/cm at room temperature. ### Claim 15 (depends on 1) The method of claim 1, further comprising a step of impregnating said anode or cathode particulates with a liquid solvent capable of dissolving said lithium salt or sodium salt to form an electrolyte. ### Claim 16 (depends on 1) The method of claim 1, wherein said electron-conducting material is selected from a conducting polymer, a carbon fiber or graphite fiber, a carbon nanotube, a carbon nanofiber, a graphitic nanofiber, a conductive polymer fiber, a metal nanowire, a metal-coated fiber, a graphene sheet, an expanded graphite platelet, carbon black, acetylene black, needle coke, or a combination thereof. ### Claim 17 (depends on 3) The method of claim 3, wherein said prelithiated graphene sheets are selected from prelithiated versions of pristine graphene, graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, chemically functionalized graphene, a physically or chemically activated or etched version thereof, or a combination thereof. ### Claim 18 (depends on 1) The method of claim 1, wherein said cathode active material contains a sodium intercalation compound or a potassium intercalation compound selected from NaFePO4, Na(1−x)KxPO4, KFePO4, Na0.7FePO4, Na1.5VOPO4F0.5, Na3V2(PO4)3, Na3V2(PO4)2F3, Na2FePO4F, NaFeF3, NaVPO4F, KVPO4F, Na3V2(PO4)2F3, Na1.5VOPO4F0.5, Na3V2(PO4)3, NaV6O15, NaxVO2, Na0.33V2O5, NaxCoO2, Na2/3[Ni1/3Mn2/3]O2, Nax(Fe1/2Mn1/2)O2, NaxMnO2, λ-MnO2, NaxK(1−x)MnO2, Na0.44MnO2, Na0.44MnO2/C, Na4Mn9O18, NaFe2Mn(PO4)3, Na2Ti3O7, Ni1/3Mn1/3CoO1/3O2, Cu0.56Ni0.44HCF, NiHCF, NaxMnO2, NaCrO2, KCrO2, Na3Ti2(PO4)3, NiCo2O4, Ni3S2/FeS2, Sb2O4, Na4Fe(CN)6/C, NaV1−xCrxPO4F, SezSy, y/z=0.01 to 100, Se, sodium polysulfide, sulfur, Alluaudites, or a combination thereof, wherein x is from 0.1 to 1.0. ### Claim 19 (depends on 1) The method of claim 1, wherein said cathode active material comprises an alkali metal intercalation compound or alkali metal-absorbing compound selected from an inorganic material, an organic or polymeric material, a metal oxide/phosphate/sulfide, or a combination thereof. ### Claim 20 (depends on 19) The method of claim 19, wherein said metal oxide/phosphate/sulfide is selected from a lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium vanadium oxide, lithium-mixed metal oxide, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium mixed metal phosphate, transition metal sulfide, transition metal fluoride, transition metal chloride, or a combination thereof. ### Claim 21 (depends on 19) The method of claim 19, wherein said inorganic material is selected from sulfur, sulfur compound, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof. ### Claim 22 (depends on 19) The method of claim 19, wherein said inorganic material is selected from TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, an iron oxide, a vanadium oxide, or a combination thereof. ### Claim 23 (depends on 19) The method of claim 19, wherein said metal oxide/phosphate/sulfide contains a vanadium oxide selected from the group consisting of VO2, LixVO2, V2O5, LixV2O5, V3O8, LixV3O8, LixV3O7, V4O9, LixV4O9, V6O13, LixV6O13, their doped versions, their derivatives, and combinations thereof, wherein 0.1