# US 10,873,083 B2 · Anode particulates or cathode particulates and 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 10,873,083 B2 - Document ID: US10873083B2 - Status: Granted - Kind: B2 - Application number: 15/860,151 - Filed: 2018-01-02 - Published: 2019-05-30 - Granted: 2020-12-22 - Earliest claimed: 2017-11-30 - Assignees: Global Graphene Group, Inc. - Applicants: Global Graphene Group, Inc. - Inventors: Aruna Zhamu; Hui He; Baofei Pan; Bor Z. Jang - Web page: https://patentgrep.com/patent/US10873083B2 ## CPC - H01M 4/60: of organic compounds - 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 4/364: {as mixtures} - H01M 4/38: of elements or alloys - H01M 4/483: {for non-aqueous cells (H01M4/485 takes precedence)} - H01M 4/523: {for non-aqueous cells (H01M4/525 takes precedence)} - H01M 4/5835: {Comprising fluorine or fluoride salts} - H01M 4/587: for inserting or intercalating light metals - H01M 4/622: {being polymers} - H01M 4/366: {as layered products} - H01M 4/386: {Silicon or alloys based on silicon} - H01M 4/387: {Tin or alloys based on tin} - H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) - H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy - 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 4/5815: {Sulfides} - H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines} - H01M 4/608: {containing heterocyclic rings} - H01M 4/624: {Electric conductive fillers} - H01M 4/625: {Carbon or graphite} - H01M 4/626: {Metals} - H01M 10/052: Li-accumulators - 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 2004/021: {Physical characteristics, e.g. porosity, surface area} - 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 an anode particulate, having a dimension from 10 nm to 300 μm, for use in an alkali metal battery, the particulate comprising (i) an anode active material capable of reversibly absorbing/desorbing lithium or sodium ions, (ii) an electron-conducting material, and (iii) a lithium or sodium salt with an optional polymer or its monomer, but without a liquid solvent, for an electrolyte, wherein the electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with the anode active material and the lithium or sodium salt is in physical contact with the anode active material (so that the salt, when later impregnated with a liquid solvent, becomes an electrolyte forming a 3D network of lithium or sodium ion-conducting channels in ionic contact with the anode active material). The particulate can be of any shape, but preferably spherical or ellipsoidal in shape. Also provided is a cathode particulate. ## Claims ### Claim 1 An anode particulate having a dimension from 10 nm to 300 μm for use in an alkali metal battery, said particulate comprising (i) an anode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, (ii) an electron-conducting material, and (iii) a lithium salt or sodium salt with an optional polymer or its monomer, but without a liquid solvent, for an electrolyte, wherein said electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with said anode active material and said lithium salt or sodium salt, when forming into an electrolyte, forms a 3D network of lithium ion- or sodium ion-conducting channels in ionic contact with said anode active material and wherein said anode particulate has an electrical conductivity from about 10−6 S/cm to about 300 S/cm. ### Claim 2 (depends on 1) The anode particulate 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 3 (depends on 1) The anode particulate 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 4 (depends on 1) The anode particulate 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 5 (depends on 1) The anode particulate 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 6 (depends on 1) The anode particulate 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 7 (depends on 1) The anode particulate of claim 1, wherein said anode active material is coated with a layer of carbon, a conducting polymer, or a graphene sheet. ### Claim 8 (depends on 1) The anode particulate of claim 1, wherein said electron-conducting polymer is selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof. ### Claim 9 (depends on 1) The anode particulate 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-Fluoro alkyl-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 10 (depends on 1) The anode particulate 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 11 (depends on 1) The anode particulate of claim 1, further comprising a resin binder. ### Claim 12 (depends on 1) The anode particulate of claim 1, wherein said electrolyte has a lithium ion conductivity or sodium ion conductivity no less than 10−7 S/cm at room temperature. ### Claim 13 (depends on 1) The anode particulate 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 14 (depends on 3) The anode particulate of claim 3, 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 15 (depends on 1) The anode particulate 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 16 (depends on 2) The anode particulate of claim 2, 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 17 (depends on 1) A powder mass containing a plurality of the anode particulates as defined in claim 1. ### Claim 18 (depends on 1) An anode containing multiple anode particulates of claim 1. ### Claim 19 (depends on 18) The anode of claim 18, wherein each particulate has an electron-conducting material forming a 3D network of electron-conducting pathways in electronic contact with the anode active material and the electrolyte in each particulate forms a 3D network of lithium ion- or sodium ion-conducting channels in ionic contact with the anode active material and wherein multiple 3D networks of electron-conducting pathways in the multiple anode particulates are merged into one large 3D network of electron-conducting pathways substantially extended throughout the entire anode and wherein multiple 3D networks of lithium ion- or sodium ion-conducting channels in the multiple anode particulates are merged into one large 3D network of lithium ion- or sodium ion-conducting channels substantially extended throughout the entire anode. ### Claim 20 (depends on 18) A lithium battery or sodium battery containing an optional anode current collector, the anode as defined in claim 18, a cathode containing a cathode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, an optional cathode current collector, an electrolyte in ionic contact with said anode and said cathode, and an optional porous separator. ### Claim 21 A cathode particulate for a lithium battery or sodium battery, wherein said cathode particulate is composed of (i) a cathode active material, (ii) an electron-conducting material, and (iii) a lithium salt or sodium salt with an optional polymer or its monomer, but without a liquid solvent, for an electrolyte, wherein the electron-conducting material forms a 3D network of electron-conducting pathways in electronic contact with the cathode active material and the lithium salt or sodium salt, when forming into said electrolyte, forms a 3D network of lithium ion- or sodium ion-conducting channels in ionic contact with the cathode active material, and wherein said cathode particulate has a dimension from 10 nm to 100 μm and an electrical conductivity from about 10−6 S/cm to about 300 S/cm. ### Claim 22 (depends on 21) A powder mass containing a plurality of the cathode particulates as defined in claim 21. ### Claim 23 (depends on 18) A cathode containing multiple cathode particulates of claim 18. ### Claim 24 (depends on 23) A lithium battery or sodium battery containing an optional anode current collector, an anode containing an anode active material capable of reversibly absorbing and desorbing lithium ions or sodium ions, the cathode as defined in claim 23, an optional cathode current collector, an electrolyte in ionic contact with said anode and said cathode, and an optional porous separator. ### Claim 25 (depends on 24) The lithium battery or sodium battery of claim 24, which is a lithium-ion battery, sodium-ion battery, lithium metal battery, sodium metal battery, lithium-sulfur battery, room temperature sodium-sulfur battery, lithium-selenium battery, sodium-air battery, or lithium-air battery. ### Claim 26 (depends on 21) The cathode particulate of claim 21, 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, Ni1/3Mn1/3Co1/3O2, 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 27 (depends on 21) The cathode particulate of claim 21, 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 28 (depends on 27) The cathode particulate of claim 27, 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 29 (depends on 27) The cathode particulate of claim 27, wherein said inorganic material is selected from sulfur, sulfur compound, lithium polysulfide, transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof. ### Claim 30 (depends on 27) The cathode particulate of claim 27, wherein said inorganic material is selected from TiS2, TaS2, MoS2, NbSe3, MnO2, CoO2, an iron oxide, a vanadium oxide, or a combination thereof. ### Claim 31 (depends on 27) The cathode particulate of claim 27, 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