# US 7,745,053 B2 · Lithium secondary battery having an improved polymer electrolyte > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,745,053 B2 - Document ID: US7745053B2 - Status: Granted - Kind: B2 - Application number: 11/406,773 - Filed: 2006-04-18 - Published: 2006-10-26 - Granted: 2010-06-29 - Earliest claimed: 2005-04-21 - Assignees: Samsung SDI Co., Ltd. - Inventors: Yong-Beom Lee; Kwang-Jo Cheong; Eui-Hwan Song - Web page: https://patentgrep.com/patent/US7745053B2 ## CPC - H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type - C08G 63/21: in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof - C08G 63/91: Polymers modified by chemical after-treatment - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - 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 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy - H01M 2300/0082: Organic polymers - Y02E 60/10: Energy storage using batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION ## Abstract Lithium secondary batteries having polymer electrolytes are provided. A lithium battery includes a positive electrode including a positive active material capable of intercalating and deintercalating lithium ions, a negative electrode including a negative active material capable of intercalating and deintercalating lithium ions, and a polymer electrolyte. The polymer electrolyte includes a polymer, a non-aqueous organic solvent, and a lithium salt. The polymer electrolyte has a shear strength relative to the positive electrode of about 0.7 N/mm or greater. ## Claims ### Claim 1 A lithium secondary battery comprising; a positive electrode comprising a positive active material capable of intercalating and deintercalating lithium ions; a negative electrode comprising a negative active material capable of intercalating and deintercalating lithium ions; and a polymer electrolyte comprising a polymer, a non-aqueous organic solvent, and a lithium salt, the polymer electrolyte having a shear strength relative to the positive electrode of about 0.7 N/mm or greater, the polymer comprising: a first monomer represented by a polyesterpolyol of Formula 1: A-polyesterpolyol-B (1) wherein the polyesterpolyol is produced by condensation of at least one alcohol derivative having from 2 to 6 OH groups and at least one dicarboxylic acid derivative, the polyesterpolyol having a weight average molecular weight ranging from about 100 to about 10,000,000, and each of A and B are linked to terminal OH groups of the polyesterpolyol, each of A and B being selected from the group consisting of CH2═CR—C(═O)—, CH2═CR—C—CH2—, CH2═CR—, CH2═CR—O—C(═O)—, CH2═CH—CH2—O—, CH2═CH—S(═O)2—, or CH2═CR—C(═O)—O—CH2CH2—NH—C(═O)—, wherein R is selected from the group consisting of C1 to C10 hydrocarbons and C6 to C10 aromatic hydrocarbons; and a second monomer selected from the group consisting of ethylene glycol methylether acrylate, Formulas 2 through 7, and combinations thereof: CH2═CR1-C(═O)—O—X (2) CH2═CR1-O—X (3) CH2═CR1-O—C(═O)—X (4) CH2═CH—CH2—O—X (5) CH2═CH—S(═O)2—X (6) CH2═CR1-C(═O)—O—CH2CH2—NH—C(═O)—O—X (7) wherein R1 is selected from the group consisting of H, C1 to C10 hydrocarbons and C1 to C10 aromatic hydrocarbons, and X is selected from the group consisting of C1 to C20 hydrocarbons, C1 to C20 halogenated hydrocarbons, C1 to C20 aromatic hydrocarbons and C1 to C20 halogenated aromatic hydrocarbons. ### Claim 2 (depends on 1) The lithium secondary battery of claim 1, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 0.7 to about 1.5 N/mm. ### Claim 3 (depends on 2) The lithium secondary battery of claim 2, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 1.0 to about 1.5 N/mm. ### Claim 4 (depends on 3) The lithium secondary battery of claim 3, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 1.2 to about 1.5 N/mm. ### Claim 5 (depends on 1) The lithium secondary battery of claim 1, wherein the at least one alcohol derivative is selected from the group consisting of polyethylene glycol, polypropylene glycol, alkanediol, ethoxylated alkanediol, propoxylated alkanediol, trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, and combinations thereof. ### Claim 6 (depends on 5) The lithium secondary battery of claim 5, wherein each of A and B is selected from the group consisting of (meth)acryl groups, vinyl groups, allyl groups, vinylsulfonyl groups, urethane(meth)acryl groups, and combinations thereof. ### Claim 7 (depends on 1) The lithium secondary battery of claim 1, wherein the second monomer is selected from the group consisting of monomers represented by Formulas 3, 6 and 7. ### Claim 8 (depends on 1) The lithium secondary battery of claim 1, wherein the lithium salt is selected from the group consisting of LiPF6, LiBF4, lithium bis(oxalato) borate, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) wherein x and y are natural numbers, LiSO3CF3, and combinations thereof. ### Claim 9 (depends on 1) The lithium secondary battery of claim 1, wherein the non-aqueous organic solvent is selected from the group consisting of carbonates, esters, ethers, ketones, nitriles, and combinations thereof. ### Claim 10 (depends on 1) The lithium secondary battery of claim 1, wherein the non-aqueous organic solvent comprises a carbonate-based solvent and an aromatic hydrocarbon-based organic solvent. ### Claim 11 (depends on 10) The lithium secondary battery of claim 10, wherein the aromatic hydrocarbon-based organic solvent is selected from the group consisting of aromatic compounds represented by Formula 9: wherein R2 is selected from the group consisting of halogens, C1 to C10 alkyls and combinations thereof, and q is an integer ranging from 0 to 6. ### Claim 12 (depends on 11) The lithium secondary battery of claim 11, wherein the aromatic hydrocarbon-based organic solvent is selected from the group consisting of benzene, fluorobenzene, toluene, fluorotoluene, trifluorotoluene, xyl ene, and combinations thereof. ### Claim 13 (depends on 1) The lithium secondary battery of claim 1, wherein the polymer electrolyte further comprises a carbonate additive selected from the group consisting of vinylene carbonate, divinylsulfone, ethylene sulfite, carbonates having substituents selected from the group consisting of halogens, cyano (CN) groups, nitro (NO2) groups and combinations thereof. ### Claim 14 (depends on 13) The lithium secondary battery of claim 13, wherein the carbonate additive is selected from the group consisting of carbonates having substituents selected from the group consisting of halogens, cyano (CN) groups and nitro (NO2) groups. ### Claim 15 (depends on 14) The lithium secondary battery of claim 14, wherein the carbonate additive is selected from the group consisting of compounds represented by Formula 10: wherein X1 is selected from the group consisting of halogens, cyano (CN) groups and nitro (NO2) groups. ### Claim 16 (depends on 15) The lithium secondary battery of claim 15, wherein the carbonate additive is fluoroethylene carbonate. ### Claim 17 A lithium secondary battery comprising: a positive electrode comprising a positive active material capable of intercalating and deintercalating lithium ions; a negative electrode including a negative active material capable of intercalating and deintercalating lithium ions; and a polymer electrolyte including a polymer, a non-aqueous organic solvent, and a lithium salt, the polymer electrolyte having a shear strength relative to the positive electrode of about 0.7 N/mm or greater and a peel strength relative to the positive electrode of about 0.002 N/mm or greater, the polymer comprising: a first monomer represented by a polyesterpolyol of Formula 1: A-polyesterpolyol-B (1) wherein the polyesterpolyol is produced by condensation of at least one alcohol derivative having from 2 to 6 OH groups and at least one dicarboxylic acid derivative, the polyesterpolyol having a weight average molecular weight ranging from about 100 to about 10,000,000, and each of A and B are linked to terminal OH groups of the polyesterpolyol, each of A and B being selected from the group consisting of CH2═CR—C(═O)—, CH2═CR—C—CH2—, CH2═CR—, CH2═CR—O—C(═O)—, CH2═CH—CH2—O—, CH2═CH—S(═O)2—, or CH2═CR—C(═)—O—CH2CH2—NH—C(═O)—, wherein R is selected from the group consisting of C1 to C10 hydrocarbons and C6 to C10 aromatic hydrocarbons; and a second monomer selected from the group consisting of ethylene glycol methylether acrylate, Formulas 2 through 7, and combinations thereof: CH2═CR1-C(═O)—O—X (2) CH2═CR1-O—X (3) CH2═CR1-O—C(═O)—X (4) CH2═CH—CH2—O—X (5) CH2═CH—S(═O)2—X (6) CH2═CR1-C(═O)—O—CH2NH—C(═O)—O—X (7) wherein R1 is selected from the group consisting of H, C1 to C10 hydrocarbons and C1 to C10 aromatic hydrocarbons, and X is selected from the group consisting of C1 to C20 hydrocarbons, C1 to 020 halogenated hydrocarbons, C1 to C10 aromatic hydrocarbons and C1 to C10 halogenated aromatic hydrocarbons. ### Claim 18 (depends on 17) The lithium secondary battery of claim 17, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 0.7 to about 1.5 N/mm and a peel strength relative to the positive electrode ranging from about 0.002 to about 0.07 N/mm. ### Claim 19 (depends on 18) The lithium secondary battery of claim 18, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 1.0 to about 0.5 N/mm and a peel strength relative to the positive electrode ranging from about 0.015 to 0.07 N/mm. ### Claim 20 (depends on 19) The lithium secondary battery of claim 19, wherein the polymer electrolyte has a shear strength relative to the positive electrode ranging from about 1.2 to about 1.5 N/mm and a peel strength relative to the positive electrode ranging from about 0.035 to 0.07 N/mm. ### Claim 21 (depends on 17) The lithium secondary battery of claim 17, wherein the at least one alcohol derivative is selected from the group consisting of polyethylene glycol, polypropylene glycol, alkanediol, ethoxylated alkanediol, propoxylated alkanediol, trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ditrimethylolpropane, ethoxylated ditrimethylolpropane, propoxylated ditrimethylolpropane, pentaerythritol, ethoxylated pentaerythritol, propoxylated pentaerythritol, dipentaerythritol, ethoxylated dipentaerythritol, propoxylated dipentaerythritol, bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, and combinations thereof. ### Claim 22 (depends on 1) The lithium secondary battery of claim 1, wherein each of A and B is selected from the group consisting of (meth)acryl groups, vinyl groups, allyl groups, vinylsulfonyl groups, urethane(meth)acryl groups, and combinations thereof. ### Claim 23 (depends on 17) The lithium secondary battery of claim 17, wherein the second monomer is selected from the group consisting of monomers represented by Formulas 3, 6 and 7. ### Claim 24 (depends on 17) The lithium secondary battery of claim 17, wherein the lithium salt is selected from the group consisting of LiPF6, LiBF4, lithium bis(oxalato) borate, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) wherein x and y are natural numbers, and LiSO3CF3. ### Claim 25 (depends on 17) The lithium secondary battery of claim 17, wherein the non-aqueous organic solvent is selected from the group consisting of carbonates, esters, ethers, ketones, nitriles, and combinations thereof. ### Claim 26 (depends on 17) The lithium secondary battery of claim 17, wherein the non-aqueous organic solvent comprises a carbonate-based solvent and an aromatic hydrocarbon-based organic solvent. ### Claim 27 (depends on 26) The lithium secondary battery of claim 26, wherein the aromatic hydrocarbon-based organic solvent is selected from the group consisting of aromatic compounds represented by Formula 9: wherein R2 is selected from the group consisting of halogens, C1 to C10 alkyls, and combinations thereof, and q is an integer ranging from 0 to 6. ### Claim 28 (depends on 27) The lithium secondary battery of claim 27, wherein the aromatic hydrocarbon-based organic solvent is selected from the group consisting of benzene, fluorobenzene, toluene, fluorotoluene, trifluorotoluene, xylene, and combinations thereof. ### Claim 29 (depends on 17) The lithium secondary battery of claim 17, wherein the electrolyte further comprises a carbonate additive selected from the group consisting of vinylene carbonate, divinylsulfone, ethylene sulfite, carbonates having substituents selected from the group consisting of halogens, cyano (CN) groups and nitro (NO2) groups, and combinations thereof. ### Claim 30 (depends on 29) The lithium secondary battery of claim 29, wherein the carbonate additive is selected from the group consisting of compounds represented by Formula 10: wherein X1 is selected from the group consisting of halogens, cyano (CN) groups, and nitro (NO2) groups. ### Claim 31 (depends on 30) The lithium secondary battery of claim 30, wherein the carbonate additive is fluoroethylene carbonate. ### Claim 32 (depends on 17) The lithium secondary battery of claim 17, wherein the negative active material is a carbon-based material. ### Claim 33 (depends on 17) The lithium secondary battery of claim 17, wherein the positive active material is a lithiated intercalation compound. ### Claim 34 A lithium secondary battery comprising: a positive electrode comprising a positive active material capable of intercalating and deintercalating lithium ions; a negative electrode comprising a negative active material capable of intercalating and deintercalating lithium ions; and a polymer electrolyte comprising a polymer, a non-aqueous organic solvent, and a lithium salt, the polymer comprising: a first monomer represented by a polyesterpolyol of Formula 1: A-polyesterpolyol-B (1) wherein the polyesterpolyol is produced by condensation of at least one alcohol derivative having from 2 to 6 OH groups and at least one dicarboxylic acid derivative, the polyesterpolyol having a weight average molecular weight ranging from about 100 to about 10,000,000, and each of A and B are linked to terminal OH groups of the polyesterpolyol, each of A and B being selected from the group consisting of CH2═CR—C(═O)—, CH2═CR—C—CH2—, CH2═CR—, CH2═CR—O—C(O)—, CH2═CH—CH2—O—, CH2CH—S(O)2—, or CH2═CR—C(═O)—O—CH2CH2—NH—C(═O)—, wherein R is selected from the group consisting of Cj to C10 hydrocarbons and C6 to C10 aromatic hydrocarbons; and a second monomer selected from the group consisting ethylene glycol methylether acrylate, Formulas 2 through 7, and combinations thereof: CH2═CR1-C(═O)—O—X (2) CH2═CR1-O—X (3) CH2═CR1-O—C(═O)—X (4) CH2═CH—CH2—O—X (5) CH2═CH—S(═O)2—X (6) CH2═CR1-C(═O)—O—CH2CH2—NH—C(═O)—O—X (7) wherein R1 is selected from the group consisting of H, C1 to C10 hydrocarbons and C1 to C10 aromatic hydrocarbons, and X is selected from the group consisting of C1 to C20 hydrocarbons, C1 to C20 halogenated hydrocarbons, C1 to C20 aromatic hydrocarbons and C1 to C20 halogenated aromatic hydrocarbons.