# US 12,191,448 B2 · Nonaqueous electrolyte solution for secondary battery, and secondary battery provided with said solution > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,191,448 B2 - Document ID: US12191448B2 - Status: Granted - Kind: B2 - Application number: 16/065,721 - Filed: 2016-12-22 - Published: 2021-07-01 - Granted: 2025-01-07 - Earliest claimed: 2015-12-25 - Assignees: Stella Chemifa Corporation - Applicants: Stella Chemifa Corporation - Inventors: Toshitaka Sakaguchi; Yoshifumi Katsura; Sojiro Kon; Masashi Yamamoto; Tetsuo Nishida - Web page: https://patentgrep.com/patent/US12191448B2 ## CPC - H01M 10/0567: characterised by the additives - 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 10/0568: characterised by the solutes - H01M 2300/0025: Organic electrolyte - H01M 2300/0037: Mixture of solvents - 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 are a nonaqueous electrolytic solution for a secondary battery that exhibits excellent cycle characteristics even in high temperature environment, and a secondary battery including the same. The nonaqueous electrolytic solution for a secondary battery of the present invention is a nonaqueous electrolyte solution for a secondary battery which is used for a secondary battery, including at least one component (A) represented by the following chemical formula (1): in which Mn+ represents at least one selected from the group consisting of a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion and an onium ion, X represents a halogen atom, R1 represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and n represents a valence. ## Claims ### Claim 1 A nonaqueous electrolytic solution for a secondary battery which is used for a secondary battery comprising an electrolyte and a nonaqueous solvent, and comprising at least one component (A) below and comprising at least one component (B) below as additives, apart from the electrolyte and the nonaqueous solvent, component (A): a compound represented by the following chemical formula (1): in which Mn+ represents at least one selected from the group consisting of a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion and an onium ion, X represents a halogen atom, R1 represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and n represents a valence, and component (B): N,N-dimethylacetoacetamide, wherein an addition amount of the component (B) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 2 (depends on 1) The nonaqueous electrolyte solution for a secondary battery according to claim 1, wherein an addition amount of the component (A) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 3 (depends on 1) The nonaqueous electrolytic solution for a secondary battery according to claim 1, wherein the component (A) is lithium ethyl monofluorophosphate. ### Claim 4 (depends on 1) A secondary battery comprising the nonaqueous electrolyte solution for a secondary battery according to claim 1, comprising a positive electrode and a negative electrode. ### Claim 5 (depends on 4) The secondary battery according to claim 4, wherein an addition amount of the component (A) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for the secondary battery. ### Claim 6 A nonaqueous electrolytic solution for a secondary battery which is used for a secondary battery comprising an electrolyte and a nonaqueous solvent, and comprising at least one component (A) below and comprising at least one of the following component (B) below as additives, apart from the electrolyte and the nonaqueous solvent, component (A): a compound represented by the following chemical formula (1): in which Mn+ represents at least one selected from the group consisting of a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion and an onium ion, X represents a halogen atom, R1 presents a hydrocarbon group having 11 to 20 carbon atoms, or a hydrocarbon group having 11 to 20 carbon atoms and having at east any one of a halogen atom, a heteroatom or an unsaturated bond, and n represents a valence, and component (B): a boron complex salt represented by the following chemical formula (2), or a boric acid ester, an acid anhydride, a cyclic carbonate having an unsaturated bond, a cyclic carbonate having a halogen atom, a cyclic sulfonic acid ester, amines having an acetoacetyl group represented by the following chemical formula (3), and at least one compound selected from the group consisting of phosphorus compounds represented by the following chemical formula (4) to (6): in which Mn+ represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion, X1 to X4 are independent of each other, and optionally selected one or two combinations form a cyclic structure of —OOC—Y—COO—, —O—Y—O— or —OOC—Y—O— in which Y represents a hydrocarbon group having 0 to 20 carbon atoms, or a hydrocarbon group having 0 to 20 carbon atoms and having a heteroatom, an unsaturated bond, or a cyclic structure, or X1 to X4 each independently represent a halogen atom, an alkyl group having 0 to 20 carbon atoms, an alkoxy group having 0 to 20 carbon atoms, an alkyl group having 0 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, or an alkoxy group having 0 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and n represents a valence, in which R2 and R3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom, a heteroatom or an unsaturated bond, in which Mn+ represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion, A1 and A2 each independently represent an oxygen atom, a sulfur atom or a selenium atom, X5 and X6 each independently represent a halogen atom, an alkyl group having 1 to 20 carton atoms, or an alkyl group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, or X5 and X6 represent any one of an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and are coupled to each other to form a cyclic structure, and n represents a valence, in which Mn+ represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion, X7 to X12 each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, an alkylthio group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, an alkylthio group having 1 to 20 carbon atoms, or an alkylthio group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, or at least one of combinations optionally selected from X7 to X12 forms a cyclic structure of —OOC—Z—COO—, —OOC—Z—O— or —O—Z—O— in which Z represents a hydrocarbon group having 0 to 20 carbon atoms, or a hydrocarbon group having 0 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom, an unsaturated bond or a cyclic structure, and n represents a valence, in which Mn+ represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion, R4 and R5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, or R4 and R5 represent any one of a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and are coupled to each other to form a cyclic structure, and n represents a valence. ### Claim 7 (depends on 6) The nonaqueous electrolytic solution for a secondary battery according to claim 6, wherein the component (B) is lithium difluorooxalatoborate, or at least one compound selected from the group consisting of N,N-dimethylacetoacetamide, lithium difluorophosphate, and phosphorus compound represented by the following chemical formula (6): in which Mn+ represents a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion or an onium ion, R4 and R5 each independently is an ethyl group or a phenyl group, and n represents a valence. ### Claim 8 (depends on 6) The nonaqueous electrolyte solution for a secondary battery according to claim 6, wherein an addition amount of the component (B) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 9 (depends on 6) A secondary battery comprising the nonaqueous electrolyte solution for a secondary battery according to claim 6, comprising a positive electrode and a negative electrode. ### Claim 10 (depends on 9) The secondary battery according to claim 9, wherein an addition amount of the component (B) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for the secondary battery. ### Claim 11 (depends on 9) The secondary battery according to claim 9, wherein an addition amount of the component (A) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for the secondary battery. ### Claim 12 (depends on 6) The nonaqueous electrolyte solution for a secondary battery according to claim 6, wherein an addition amount of the component (A) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 13 A nonaqueous electrolytic solution for a secondary battery which is used for a secondary battery comprising an electrolyte and a nonaqueous solvent, and comprising at least one component (A) below and comprising at least one component (B) below as additives, apart from the electrolyte and the nonaqueous solvent, component (A): a compound represented by the following chemical formula (1): in which Mn+ represents at least one selected from the group consisting of a hydrogen ion, a sodium ion, a potassium ion, a rubidium ion, a cesium ion, an alkaline earth metal ion, an aluminum ion, a transition metal ion and an onium ion, X represents a halogen atom, R1 represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and having at least any one of a halogen atom, a heteroatom or an unsaturated bond, and n represents a valence, and component (B): N,N-dimethylacetoacetamide, wherein an addition amount of the component (B) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 14 (depends on 13) The nonaqueous electrolyte solution for a secondary battery according to claim 13, wherein an addition amount of the component (A) is 0.05% by mass to 5% by mass of a total mass of the nonaqueous electrolyte solution for a secondary battery. ### Claim 15 (depends on 13) A secondary battery comprising the nonaqueous electrolyte solution for a secondary battery according to claim 13, comprising a positive electrode and a negative electrode.