# US 10,374,232 B2 · Complexometric precursor formulation methodology for industrial production of fine and ultrafine powders and nanopowders for lithium metal oxides for battery applications > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,374,232 B2 - Document ID: US10374232B2 - Status: Granted - Kind: B2 - Application number: 13/842,278 - Filed: 2013-03-15 - Published: 2014-09-18 - Granted: 2019-08-06 - Earliest claimed: 2013-03-15 - Assignees: Nano One Materials Corp. - Applicants: Nano One Materials Corp. - Inventors: Teresita Frianeza-Kullberg - Web page: https://patentgrep.com/patent/US10374232B2 ## CPC - 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 - C01B 25/45: containing plural metal, or metal and ammonium - C01G 45/1242: of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4 - C01G 51/42: containing alkali metals, e.g. LiCoO2 - C01G 53/42: containing alkali metals, e.g. LiNiO2 - C01G 53/502: containing lithium and cobalt - H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy - C01P 2002/52: containing elements as dopants - C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram - C01P 2004/03: obtained by SEM - C01P 2004/62: Submicrometer sized, i.e. from 0.1-1 micrometer - C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer - C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases - C01P 2006/12: Surface area - C01P 2006/40: Electric properties - 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) - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20) - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A compound MjXp which is particularly suitable for use in a battery prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j is an integer representing the moles of said positive ion per moles of said MjXp; and Xp, a negative anion or polyanion from Groups IIIA, IV A, VA, VIA and VIIA and may be one or more anion or polyanion and p is an integer representing the moles of said negative ion per moles of said MjXp. ## Claims ### Claim 1 A compound MjXp prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j represents the moles of said positive ion per mole of said MjXp; and Xp is an anion or polyanion selected from the group consisting of at least one anion or polyanion of Groups IIIA, IVA, VA, VIA and VIIA; and p represents the moles of said anion or polyanion per mole of said MjXp; wherein said compound has a particle size of less than 1 micron and said compound has a surface area of at least 1 m2/gm and wherein said compound is a layered nanostructure wherein said Mj comprises M1 and M2 and wherein M1 is lithium and M2 is a transition metal wherein said transition metal is selected from the group consisting of Ni, Mn and Co and wherein said compound has the formula LiMnxCoyNizO2 wherein x+y+z≤1. ### Claim 2 (depends on 1) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 1 wherein said compound is Li2-x-y-zNixMnyCozO2 wherein x+y+z≤1 and at least one of said x, y or z is not zero. ### Claim 3 (depends on 2) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 2 wherein said compound is Li2-x-y-zNixMnyCozO2 wherein x+y+z≤1 and none of said x, y or z are zero. ### Claim 4 (depends on 1) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 1 further comprising a dopant. ### Claim 5 (depends on 4) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 4 wherein said dopant is selected from the group consisting of alkali or alkaline earth metals, Group III A, IV A and transition metals. ### Claim 6 (depends on 4) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 4 comprising up to 10 weight % of said dopant. ### Claim 7 (depends on 1) The compound MjXp prepared by the complexometric precursor formulation methodology of claim 1 wherein said compound has a particle size of 100 to 300 nm. ### Claim 8 A compound MjXp prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j represents the moles of said positive ion per mole of said MjXp; and Xp is an anion or polyanion selected from the group consisting of at least one anion or polyanion of Groups IIIA, IVA, VA, VIA and VIIA; and p represents the moles of said anion or polyanion per mole of said MjXp; wherein said compound has a particle size of less than 1 micron and said compound has a surface area of at least 1 m2/gm and wherein said compound is a layered nanostructure selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and lithium mixed oxides of cobalt, nickel and manganese. ### Claim 9 A composition comprising a compound MjXp prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j represents the moles of said positive ion per mole of said MjXp; and Xp is an anion or polyanion selected from the group consisting of at least one anion or polyanion of Groups IIIA, IVA, VA, VIA and VIIA; and p represents the moles of said anion or polyanion per mole of said MjXp; wherein said compound has a particle size of less than 1 micron and said compound has a surface area of at least 1 m2/gm and wherein said compound is in a layered nanostructure with a coating on said compound and wherein said compound has the formula LiMnxCoyNizO2 wherein x+y+z≤1. ### Claim 10 (depends on 9) The composition of claim 9 wherein said coating comprises alkali or alkaline earth metals, Group III A and IV A and transition metals. ### Claim 11 (depends on 9) The composition of claim 9 wherein said coating comprises an organic or inorganic compound. ### Claim 12 (depends on 11) The composition of claim 11 wherein said coating is a MjXp compound prepared by complexometric precursor formulation methodology. ### Claim 13 (depends on 11) The composition of claim 11 wherein said coating is a nanolayer. ### Claim 14 (depends on 11) The composition of claim 11 wherein said coating comprises carbon or a carbon-containing compound. ### Claim 15 A battery comprising a compound MjXp prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j represents the moles of said positive ion per mole of said MjXp; and Xp is an anion or polyanion selected from the group consisting of at least one anion or polyanion of Groups IIIA, IVA, VA, VIA and VIIA; and p represents the moles of said anion or polyanion per mole of said MjXp; wherein said compound has a particle size of less than 1 micron and said compound has a surface area of at least 1 m2/gm and wherein said compound is in a layered nanostructure and wherein said compound has the formula LiMnxCoyNizO2 wherein x+y+z≤1. ### Claim 16 (depends on 15) The battery of claim 15 wherein said compound is defined by the formula Li2-x-y-zNixMnyCozO2 wherein x+y+z≤1 and at least one of x, y or z is not zero. ### Claim 17 (depends on 15) The battery of claim 15 wherein said compound is Li2-x-y-zNixMnyCozO2 wherein x+y+z≤1 and none of x, y or z are zero. ### Claim 18 (depends on 15) The battery of claim 15 having a capacity of at least 80 mAh/g after 500 cycles at room temperature at a discharge rate of 1 C when discharged from 4.2 volts to 3 volts. ### Claim 19 (depends on 15) The battery of claim 15 having a capacity of 150 mAh/g after 500 cycles at room temperature at a discharge rate of 1 C when discharged from 4.6 volts to 2.5 volts. ### Claim 20 A composition comprising a compound MjXp prepared by the complexometric precursor formulation methodology wherein: Mj is at least one positive ion selected from the group consisting of alkali metals, alkaline earth metals and transition metals and j represents the moles of said positive ion per mole of said MjXp; and Xp is an anion or polyanion selected from the group consisting of at least one anion or polyanion of Groups IIIA, IVA, VA, VIA and VIIA; and p represents the moles of said anion or polyanion per mole of said MjXp; wherein said Mj comprises M1 and M2 and wherein M1 is lithium and M2 is a transition metal and wherein said compound has a particle size of less than 50 microns, said compound has a surface area of at least 1 m2/gm, said compound is in a layered nanostructure and wherein said compound has the formula LiMnxCoyNizO2 wherein x+y+z≤1. ### Claim 21 (depends on 20) The composition comprising a compound MiXp prepared by the complexometric precursor formulation methodology of claim 20 wherein said compound has a particle size of 100 to 300 nm.