# US 11,444,318 B2 · Garnet-type lithium-ion solid-state conductor > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,444,318 B2 - Document ID: US11444318B2 - Status: Granted - Kind: B2 - Application number: 16/541,255 - Filed: 2019-08-15 - Published: 2020-07-16 - Granted: 2022-09-13 - Earliest claimed: 2019-01-11 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Yan Wang; Lincoln Miara; Sang Bok Ma - Web page: https://patentgrep.com/patent/US11444318B2 ## CPC - C01G 35/006: {Compounds containing tantalum, with or without oxygen or hydrogen, and containing two or more other elements} - H01M 10/0562: Solid materials - C01G 27/006: {Compounds containing hafnium, with or without oxygen or hydrogen, and containing two or more other elements} - C04B 35/486: Fine ceramics - C04B 35/495: based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates - C04B 35/50: based on rare-earth compounds {(non-oxide rare earth compounds C04B35/5156)} - C04B 35/505: based on yttrium oxide - C04B 35/553: based on fluorides - C04B 35/6262: {of calcined, sintered clinker or ceramics} - H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx - H01M 4/134: Electrodes based on metals, Si or alloys - H01M 4/382: {Lithium (H01M4/405 takes precedence)} - H01M 4/622: {being polymers} - 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 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes - H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)} - H01M 50/443: Particulate material - H01M 50/451: comprising layers of only organic material and layers containing inorganic material - H01M 50/497: Ionic conductivity - C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram - C01P 2004/32: Spheres - C01P 2004/60: Particles characterised by their size - C01P 2006/14: Pore volume - C01P 2006/16: Pore diameter - C01P 2006/40: Electric properties - C04B 2235/3201: Alkali metal oxides or oxide-forming salts thereof - C04B 2235/3203: Lithium oxide or oxide-forming salts thereof - C04B 2235/3206: Magnesium oxides or oxide-forming salts thereof - C04B 2235/3208: Calcium oxide or oxide-forming salts thereof, e.g. lime - C04B 2235/3213: Strontium oxides or oxide-forming salts thereof - C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina - C04B 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide - C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof - C04B 2235/3227: Lanthanum oxide or oxide-forming salts thereof - C04B 2235/3229: Cerium oxides or oxide-forming salts thereof - C04B 2235/3232: Titanium oxides or titanates, e.g. rutile or anatase - C04B 2235/3251: Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof - C04B 2235/3286: Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate - C04B 2235/3293: Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO] - C04B 2235/3296: Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate - C04B 2235/3409: Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax - C04B 2235/3418: Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint - C04B 2235/6567: Treatment time - C04B 2235/6587: Influencing the atmosphere by vaporising a solid material, e.g. by using a burying of sacrificial powder - C04B 2235/80: Phases present in the sintered or melt-cast ceramic products other than the main phase - C04B 2235/96: Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance - H01M 2004/027: {Negative electrodes} - H01M 2004/028: {Positive electrodes} - H01M 2300/0068: inorganic - H01M 2300/0071: Oxides - H01M 2300/0094: in the form of layered products, e.g. coatings - 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) - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS ## Abstract Disclosed is a solid state electrolyte comprising a compound of Formula 1 Li7−a*α−(b−4)*β−xMaαLa3Hf2−βMbβO12−x−δXx (1) wherein Ma is a cationic element having a valence of a+; Mb is a cationic element having a valence of b+; and X is an anion having a valence of −1, wherein, when Ma includes H, 0≤α≤5, otherwise 0≤α≤0.75, and wherein 0≤β≤1.5, 0≤x≤1.5, and (a*α+(b−4)β+x)>0, 0≤δ≤1. ## Claims ### Claim 1 A solid state electrolyte comprising a compound of Formula 1 Li7−a*α−(b−4)*β−xMaαLa3Hf2−βMbβO12−x−δXx (1) wherein Ma is a cationic element having a valence of a+; Mb is a cationic element having a valence of b+; and X is an anion having a valence of −1, wherein, when Ma comprises H, 0<α≤5, otherwise 0<α≤0.75, and wherein 0≤β≤1.5, 00, 0≤δ≤1. ### Claim 2 (depends on 1) The solid state electrolyte of claim 1, wherein a Li crystallographic site comprises Ma disposed thereon. ### Claim 3 (depends on 1) The solid state electrolyte of claim 1, wherein Ma is a monovalent element, a divalent element, a trivalent element, or a tetravalent element. ### Claim 4 (depends on 2) The solid state electrolyte of claim 2, wherein a is 1 and Ma is monovalent and is H, Na, K, Rb, or a combination thereof. ### Claim 5 (depends on 2) The solid state electrolyte of claim 2, wherein a is 2 and Ma is divalent and is Be, Mg, Ca, Sr, Ba, or a combination thereof. ### Claim 6 (depends on 2) The solid state electrolyte of claim 2, wherein a is 3, and Ma is trivalent and is B, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, or a combination thereof. ### Claim 7 (depends on 2) The solid state electrolyte of claim 2, wherein a is 4, and Ma is tetravalent and is Zr, Ti, Sn, Si, Ge, Pb, or a combination thereof. ### Claim 8 (depends on 1) The solid state electrolyte of claim 1, wherein a Hf crystallographic site comprises Mb disposed thereon. ### Claim 9 (depends on 1) The solid state electrolyte of claim 1, wherein Mb is a divalent element, a trivalent element, a tetravalent element, or a pentavalent element. ### Claim 10 (depends on 9) The solid state electrolyte of claim 9, wherein b is 2 and Mb is divalent and is Be, Mg, Ca, Sr, Ba, or a combination thereof. ### Claim 11 (depends on 9) The solid state electrolyte of claim 9, wherein b is 3 and Mb is trivalent and is B, Al, Ga, In, Sc, Y, La, Ce, Pr, Nd, or a combination thereof. ### Claim 12 (depends on 9) The solid state electrolyte of claim 9, wherein b is 4 and Mb is tetravalent and is Zr, Ti, Sn, Si, Ge, Pb, or a combination thereof. ### Claim 13 (depends on 9) The solid state electrolyte of claim 9, wherein b is 5 and Mb is pentavalent and is V, Ta, Nb, or a combination thereof. ### Claim 14 (depends on 9) The solid state electrolyte of claim 9, wherein b is 6 and Mb is hexavalent and is Cr, Mo, W, or a combination thereof. ### Claim 15 (depends on 1) The solid state electrolyte of claim 1, wherein Ma and Mb are different. ### Claim 16 (depends on 1) The solid state electrolyte of claim 1, wherein X is F. ### Claim 17 (depends on 1) The solid state electrolyte of claim 1, wherein Mb is Zr, and wherein the solid state electrolyte is in the form of a particle wherein a ratio of a concentration of Hf to Zr on a surface of the particle is greater than a ratio of a concentration of Hf to Zr in a center of the particle. ### Claim 18 (depends on 1) The solid state electrolyte of claim 1, wherein Mb is Zr, and wherein the solid state electrolyte is in the form of a particle wherein a concentration of Hf increases in a direction from a center of the particle to a surface of the particle. ### Claim 19 (depends on 1) A particle comprising: the solid state electrolyte of claim 1; and a liquid electrolyte within a pore of the particle. ### Claim 20 (depends on 1) A solid state electrolyte comprising: a core comprising a first solid state electrolyte; and a shell comprising the compound of claim 1 on the core, wherein the first solid state electrolyte and the compound of Formula 1 are different. ### Claim 21 (depends on 1) A porous separator for a battery, the separator comprising: a porous substrate, and the compound of claim 1 on the substrate. ### Claim 22 (depends on 1) A protected negative electrode, the electrode comprising lithium metal and the solid state electrolyte of claim 1 directly on the lithium metal. ### Claim 23 (depends on 1) A positive active material for a lithium battery, the positive active material comprising: a lithium transition metal oxide; and the solid state electrolyte of claim 1 on the lithium transition metal oxide. ### Claim 24 (depends on 1) A battery comprising: a positive electrode; a negative electrode; and the solid state electrolyte of claim 1 between the positive electrode and the negative electrode. ### Claim 25 A solid state electrolyte comprising a compound of the formula Li7−a*α−(b−4)*β−xMaαLa3Hf2−βMbβO12−x−δFx wherein Ma is a cationic element having a valence of a+; Mb is a cationic element having a valence of b+; and wherein, when Ma comprises H, 0<α≤5, otherwise 0<α≤0.75, and wherein 0≤β≤1.5, 00, 0≤δ≤1.