# US 11,909,037 B2 · Positive electrode and lithium battery including the same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,909,037 B2 - Document ID: US11909037B2 - Status: Granted - Kind: B2 - Application number: 18/060,681 - Filed: 2022-12-01 - Published: 2023-04-06 - Granted: 2024-02-20 - Earliest claimed: 2018-12-21 - Assignees: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd. - Applicants: Samsung Electronics Co., Ltd.; Samsung SDI Co., Ltd. - Inventors: Hongsoo Choi; Hyeokjo Gwon; Soyeon Kim; Hyunseok Kim; Wonseok Chang - Web page: https://patentgrep.com/patent/US11909037B2 ## CPC - C08F 212/08: Styrene - H01M 4/382: {Lithium (H01M4/405 takes precedence)} - C08F 8/32: by reaction with amines - C08F 12/26: Nitrogen - C08F 212/18: {Chlorine} - C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen - H01M 4/13: Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof - H01M 4/366: {as layered products} - 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 4/62: Selection of inactive substances as ingredients for active masses, e.g. binders, fillers - 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 10/0562: Solid materials - H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type - H01M 2004/027: {Negative electrodes} - H01M 2004/028: {Positive electrodes} - Y02E 60/10: Energy storage using batteries - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract A positive electrode includes a composite material including a positive active material and a coating layer on a surface of the positive active material, wherein the coating layer includes a copolymer including a first repeating unit represented by Formula 1 below and a second repeating unit represented by Formula 2 below: wherein Ar1, R1 to R6, A, A1, Y−, m, and n are the same as defined in the specification. ## Claims ### Claim 1 A positive electrode for a lithium battery comprising: a composite material comprising a positive active material as a core of the composite material, and a coating layer located on a surface of the positive active material forming a shell on the core of the composite material, wherein the coating layer comprises a copolymer comprising a first repeating unit represented by Formula 1, and a second repeating unit represented by Formula 2: wherein in Formula 1, Ar1 is a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C6-C30 heteroarylene group, R1, R2, and R3 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group, A is a bond, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C4-C30 cycloalkylene group, or a substituted or unsubstituted C3-C30 heterocycloalkylene group, is a 3-membered to 31-membered ring system comprising 2 to 30 carbon atoms, and X is —S, —N(R), or —P(R′), R and R′ are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C7-C30 arylalkyl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C4-C30 heteroarylalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C3-C30 alkynyl group, and Y− is an anion, wherein in Formula 2, A1 is —C(═O)O—(CH2CH2O)a—R7, wherein R7 is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, or a substituted or unsubstituted C6-C30 aryl group, and a is an integer of 1 to 10, and R4, R5, and R6 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group, and in Formulae 1 and 2, m and n are mole fractions of the first repeating unit represented by Formula 1 and the second repeating unit represented by Formula 2, respectively, wherein a sum of m and n is 1, and m and n are each independently greater than 0 and less than 1. ### Claim 2 (depends on 1) The positive electrode of claim 1, wherein Ar1 of Formula 1 comprises a phenylene group, a biphenylene group, a naphthalenylene group, a phenanthrenylene group, a triphenlylenylene group, an anthracenylene group, a fluorenylene group, or a carbazolylene group. ### Claim 3 (depends on 1) The positive electrode of claim 1, wherein Ar1 of Formula 1 is one of the groups represented by Formula 3-1, Formula 3-2, Formula 3-3, Formula 3-3, Formula 3-4, or Formula 3-5 below: wherein in Formula 3-1, Formula 3-2, Formula 3-3, Formula 3-4, and Formula 3-5, * is a point of attachment, and R11 to R20 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group. ### Claim 4 (depends on 1) The positive electrode of claim 1, wherein of Formula 1 comprises a group represented by Formula 4-1, Formula 4-2, Formula 4-3, Formula 4-4, or Formula 4a: wherein in Formula 4-1, Formula 4-2, Formula 4-3, and Formula 4-4, Z is S, N, or P, and R11 to R25 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heteroaryloxy group, a substituted or unsubstituted C4-C30 cycloalkyl group, or a substituted or unsubstituted C3-C30 heterocycloalkyl group, wherein R11 is absent when Z is S, wherein in Formula 4a, R22 to R26 are defined the same as R11 to R25 of Formula 4-1, Formula 4-2, Formula 4-3, Formula 4-4, and Z is N. ### Claim 5 (depends on 1) The positive electrode of claim 1, wherein of Formula 1 comprises a group represented by Formula 5-1 or Formula 5-2, and Y− in Formula 1 comprises BF4−, PF6−, AsF6−, SbF6−, AlCl4−, HSO4−, CH3SO3−, (CF3SO2)2N−, Cl−, Br−, I−, SO4−, ClO4−, CF3SO3−, CF3CO2−, (C2F5SO2)2N−, (C2F5SO2)(CF3SO2)N−, (FSO2)2N−, NO3−, Al2Cl7−, CH3COO−, (CF3SO2)3C−, (CF3)2PF4−, (CF3)3PF3−, (CF3)4PF2−, (CF3)5PF−, (CF3)6P−, SF5CF2SO3−, SF5CHFCF2SO3−, CF3CF2(CF3)2CO−, (CF3SO2)2CH−, (SF5)3C−, (O(CF3)2C2(CF3)2O)2PO−, or a combination thereof: wherein in Formula 5-1 and Formula 5-2, R20 to R28 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heteroaryloxy group, a substituted or unsubstituted C4-C30 cycloalkyl group, or a substituted or unsubstituted C3-C30 heterocycloalkyl group. ### Claim 6 (depends on 1) The positive electrode of claim 1, wherein an amount of the copolymer in the coating layer is from about 0.1 parts by weight to about 10 parts by weight, based on 100 parts by weight of a total weight of the positive electrode. ### Claim 7 (depends on 1) The positive electrode of claim 1, wherein the copolymer comprises a random copolymer, and wherein the copolymer has a degree of polymerization of about 10 to about 5,000. ### Claim 8 (depends on 1) The positive electrode of claim 1, wherein a molar ratio of m to n in Formula 1 is from about 2:8 to about 5:5. ### Claim 9 (depends on 1) The positive electrode of claim 1, wherein the copolymer is represented by Formula 7 below, and has a degree of polymerization of about 10 to about 5,000: wherein in Formula 7, Ar1 is a substituted or unsubstituted C6-C30 arylene group, R1 to R6 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group, A is a bond, a substituted or unsubstituted C1-C30 alkylene group, or a substituted or unsubstituted C6-C30 arylene group, Y− comprises BF4−, PF6−, AsF6−, SbF6−, AlCl4−, HSO4−, CH3SO3−, (CF3SO2)2N−, Cl−, Br−, I−, SO4−, ClO4−, CF3SO3−, CF3CO2−, (C2F5SO2)2N−, (C2F5SO2)(CF3SO2)N−, (FSO2)2N−, NO3−, Al2Cl7−, CH3COO−, (CF3SO2)3C−, (CF3)2PF4−, (CF3)3PF3−, (CF3)4PF2−, (CF3)5PF−, (CF3)6P−, SF5CF2SO3−, SF5CHFCF2SO3−, CF3CF2(CF3)2CO−, (CF3SO2)2CH−, (SF5)3C−, (O(CF3)2C2(CF3)2O)2PO−, or a combination thereof, m and n are each independently from 0.01 to 0.99, wherein a sum of m and n is 1, R7 is hydrogen, a substituted or unsubstituted C1-C30 alkyl group, or a substituted or unsubstituted C6-C30 aryl group, and a is an integer of 1 to 10, and comprises a group represented by Formula 5-1 or Formula 5-2 below, wherein in Formula 5-1 and Formula 5-2, R20 to R28 are each independently hydrogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heteroaryloxy group, a substituted or unsubstituted C4-C30 cycloalkyl group, or a substituted or unsubstituted C3-C30 heterocycloalkyl group, and * is a point of attachment. ### Claim 10 (depends on 1) The positive electrode of claim 1, wherein the copolymer comprises a compound represented by Formula 12, Formula 13, Formula 14, Formula 15, or a combination thereof, and a degree of polymerization of the copolymer is a about 10 to about 5,000: wherein in Formulas 12 to 15, Y− comprises PF6−, AsF6−, SbF6−, AlCl4−, HSO4−, CH3SO3−, (CF3SO2)2N−, Cl−, Br−, I−, SO4−, ClO4−, CF3SO3−, CF3CO2−, (C2F5SO2)2N−, (C2F5SO2)(CF3SO2)N−, (FSO2)2N−, NO3−, Al2Cl7−, CH3COO−, (CF3SO2)3C−, (CF3)2PF4−, (CF3)3PF3−, (CF3)4PF2−, (CF3)5PF−, (CF3)6P−, SF5CF2SO3−, SF5CHFCF2SO3−, CF3CF2(CF3)2CO−, (CF3SO2)2CH−, (SF5)3C−, (O(CF3)2C2(CF3)2O)2PO−, or a combination thereof, a is an integer of 1 to 10, R24 is a C1-C10 alkyl group, m and n are each independently 0.01 to 0.99, wherein a sum of m and n is 1, and the copolymer has a degree of polymerization of about 10 to about 5000. ### Claim 11 (depends on 1) The positive electrode of claim 1, wherein the positive active material comprises a lithium nickel manganese oxide, a lithium cobalt oxide, a lithium nickel cobalt manganese oxide, a lithium nickel cobalt aluminum oxide, a lithium phosphate iron oxide, an overlithiated layered oxide, or a combination thereof. ### Claim 12 (depends on 1) The positive electrode of claim 1, wherein the coating layer further comprises a lithium salt, wherein an amount of the lithium salt is in a range of about 0.1 part by weight to about 90 parts by weight, based on 100 parts by weight of the coating layer, and wherein the lithium salt comprises LiSCN, LiN(CN)2, Li(CF3SO2)3C, LiC4F9SO3, LiN(SO2CF2CF3)2, LiCl, LiF, LiBr, LiI, LiB(C2O4)2, LiBF4, LiBF3(C2F5), lithium bis(oxalato) borate, lithium oxalyldifluoroborate, lithium difluoro(oxalato)borate, lithium bis(trifluoro methanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, LiCF3SO3, LiAsF6, LiSbF6, LiClO4, or a combination thereof. ### Claim 13 (depends on 1) The positive electrode of claim 1, wherein the coating layer has a thickness of about 0.1 nanometer to about 100 nanometers. ### Claim 14 (depends on 1) The positive electrode of claim 1, further comprising a binder comprising a sulfide electrolyte, an oxide electrolyte, or a combination thereof, and the sulfide electrolyte comprises a compound represented by Formula 16 below: LiaMbPScAd Formula 16 wherein in Formula 16, 0