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Non-Aqueous Electrolyte and Secondary Cell Using the Same (19) TZZ_¥_Z_¥_T (11) EP 1 317 013 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: H01M 4/02 (2006.01) H01M 4/58 (2010.01) 15.03.2017 Bulletin 2017/11 H01M 4/48 (2010.01) (21) Application number: 02745873.6 (86) International application number: PCT/JP2002/006906 (22) Date of filing: 08.07.2002 (87) International publication number: WO 2003/007416 (23.01.2003 Gazette 2003/04) (54) NON-AQUEOUS ELECTROLYTE AND SECONDARY CELL USING THE SAME NICHTWÄSSRIGER ELEKTROLYT UND DIESEN VERWENDENDE SEKUNDÄRZELLE ELECTROLYTE NON AQUEUX ET CELLULE SECONDAIRE UTILISANT CET ELECTROLYTE (84) Designated Contracting States: •UE,M., DE Mitsubishi Chemical Corporation Inashiki-gun, (30) Priority: 10.07.2001 JP 2001208992 Ibaraki 300-0332 (JP) 16.07.2001 JP 2001214638 • SUZUKI, H., Mitsubishi Chemical Corporation (43) Date of publication of application: Inashiki-gun, 04.06.2003 Bulletin 2003/23 Ibaraki 300-0332 (JP) (73) Proprietor: Mitsubishi Chemical Corporation (74) Representative: Vossius & Partner Chiyoda-ku Patentanwälte Rechtsanwälte mbB Tokyo 100-8251 (JP) Siebertstrasse 3 81675 München (DE) (72) Inventors: • TAKEHARA, M., (56) References cited: Mitsubishi Chemical Corporation EP-A- 0 997 960 EP-A- 1 199 765 Inashiki-gun, JP-A- 5 315 006 JP-A- 5 315 006 Ibaraki 300-0332 (JP) JP-A- 7 105 977 JP-A- 7 211 351 • FUJII, T., JP-A- 7 283 083 JP-A- 7 283 083 Mitsubishi Chemical Corporation JP-A- 8 321 438 JP-A- 8 321 440 Inashiki-gun, JP-A- 9 106 833 JP-A- 10 050 344 Ibaraki 300-0332 (JP) JP-A- 10 270 075 JP-A- 11 185 810 • KOTATO, M., JP-A- 11 185 810 JP-A- 62 111 976 Mitsubishi Chemical Corporation JP-A- 62 217 578 JP-A- 63 126 871 Inashiki-gun, JP-A- 2000 235 868 JP-A- 2000 235 868 Ibaraki 300-0332 (JP) JP-A- 2001 052 741 JP-A- 2001 060 464 • NODA, D., JP-A- 2001 126 762 US-A- 5 731 106 Mitsubishi Chemical Corporation US-A- 5 731 106 US-A- 6 045 945 Inashiki-gun, Ibaraki 300-0332 (JP) •KINOSHITA,S., Mitsubishi Chemical Corporation Inashiki-gun, Ibaraki 300-0332 (JP) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 317 013 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 317 013 B1 Description <Technical Field> 5 [0001] The present invention relates to a nonaqueous electrolyte solution and a secondary battery employing the same. More particularly, the invention relates to a specific nonaqueous electrolyte solution and a nonaqueous-electrolyte- solution secondary battery which, because of the electrolyte solution employed therein, is excellent in high-temperature storage characteristics, cycle characteristics, and capacity retention characteristics and in various cell characteristics in a wide temperature range and safety such as firing properties and has a high energy density. 10 <Background Art> [0002] With the recent trend toward weight reduction and size reduction in electrical products, the desire for develop- ment of a lithium secondary battery having a high energy density is becoming stronger than before. There also is a 15 desire for improvements in various cell characteristics as a result of the spread of fields to which lithium secondary batteries are applied. [0003] Nonaqueous-electrolyte-solution secondary batteries presently proposed employ a metal oxide salt such as LiCoO2, Li2Mn2O4, or LiNiO2 for the positive electrode and further employ lithium metal or a compound capable of occluding and releasing lithium ions, such as a carbonaceous material, e.g., coke, artificial graphite, or natural graphite, 20 or a metal oxide material, e.g., an oxide of Sn or Si, for the negative electrode. [0004] In those nonaqueous-electrolyte-solution secondary batteries, ethylene carbonate is frequently used as the main solvent for the electrolyte solutions because of the high permittivity thereof. However, since ethylene carbonate has a high solidifying point, is solid at room temperature when used alone, and has a high viscosity, the electrolyte solutions employing ethylene carbonate as a solvent usually are ones in which the ethylene carbonate is used as a 25 mixed solvent containing as a co-solvent a low-viscosity solvent such as a dialkyl carbonate, e.g., diethyl carbonate. However, since low-viscosity solvents generally have a low boiling point and a low permittivity, addition thereof in a large amount not only reduces the degree of dissociation of the lithium salt, resulting in reduced electrolyte solution perform- ances, but also poses problems concerning salt precipitation caused by solvent volatilization, safety due to a lowered flash point, etc. Conversely, addition in too small an amount poses problems concerning low-temperature electrical 30 conductivity and viscosity. [0005] On the other hand, lactone compounds such as γ-butyrolactone have a sufficiently high permittivity, although inferior to ethylene carbonate, and have a low solidifying point and low viscosity. Such lactone compounds can hence exhibit sufficient electrolyte solution performances without being mixed with a low-viscosity solvent. As a result, such lactone compounds are excellent solvents which compare favorably in performance with electrolyte solutions employing 35 a solvent obtained by mixing ethylene carbonate with a low-viscosity solvent. [0006] Consequently, an electrolyte solution employing γ-butyrolactone as the main solvent and containing as a co- solvent about from 15 to 35% by volume ethylene carbonate and a nonaqueous-electrolyte-solution secondary battery employing this electrolyte solution have been proposed (Japanese Patent Laid-Open No. 31525/1999). [0007] However, the electrolyte solution employing γ-butyrolactone is inferior in electrochemical oxidation resistance 40 and reduction resistance to the electrolyte solutions employing a solvent obtained by mixing ethylene carbonate with a low-viscosity solvent. The γ-butyrolactone-based electrolyte solution hence has problems concerning, e.g., cell capacity retention at high temperatures, and a further improvement has been desired. <Disclosure of the Invention> [0008] An object of the invention is to provide a nonaqueous-electrolyte-solution secondary battery which employs a lactone compound as a nonaqueous solvent and which has been improved in high-temperature cell capacity retention, 45 etc., is excellent in various cell characteristics in a wide temperature range and safety such as firing properties, and has a high energy density. [0009] It is known that a lactone compound, when it contains water, undergoes equilibrium reactions in which part thereof reacts with water to undergo ring cleavage and thereby yield a chain hydroxy carboxylic acid compound. [0010] It has hence been presumed as a matter of course that a hydroxy carboxylic acid is contained also in electrolyte 50 solutions containing a lactone compound. However, no report has been made to the effect that the content of the acid in an electrolyte solution was precisely determined and the relationship between this content and cell performances was examined. Especially in electrolyte solutions containing an Li salt, not only there is a fear that the water content therein may be higher than in the lactone compound itself used because of inclusion of the salt, but also there is a possibility that an equilibrium reaction might proceed further due to the influence of the Li salt. 55 [0011] The present inventors have found that in an electrolyte solution employing a nonaqueous solvent mainly com- prising a lactone compound, the electrochemical oxidation resistance-reduction resistance of this electrolyte solution, which contains a hydroxy carboxylic acid, deteriorates with increasing hydroxy carboxylic acid amount and this impairs the cell performances and is a cause of a decrease in high-temperature capacity retention. As a result of further intensive 2 EP 1 317 013 B1 investigations, it has been found that the problems can be mitigated by regulating the total content of such hydroxy carboxylic acids to a specific amount. The invention has been thus completed. [0012] Namely, an essential point of the invention resides in a nonaqueous electrolyte solution for secondary batteries which is an electrolyte solution for secondary batteries obtained by dissolving a lithium salt in a nonaqueous solvent, 5 characterized in that the nonaqueous solvent is a solvent mainly comprising a lactone compound and the content of hydroxy carboxylic acids in the electrolyte solution is 0.1 mmol/kg to 0.5 mmol/kg. [0013] Another essential point of the invention resides in a nonaqueous-electrolyte-solution secondary battery com- prising at least a negative electrode comprising lithium metal, a lithium alloy, or a material capable of occluding and releasing lithium, a positive electrode comprising a material capable of occluding and releasing lithium, and an electrolyte 10 solution obtained by dissolving a lithium salt in a nonaqueous solvent, characterized in that the nonaqueous solvent is a solvent mainly comprising a lactone compound and the content of hydroxy carboxylic acids in the electrolyte solution is 0.1 mmol/kg to 0.5 mmol/Kg. <Best Mode for Carrying Out the Invention> 15 [0014] Modes for carrying out the invention will be explained below in detail. [0015] The nonaqueous electrolyte solution of the invention is an electrolyte solution for secondary batteries which is obtained by dissolving a lithium salt in a nonaqueous solvent, and is characterized in that the nonaqueous solvent is a solvent mainly comprising a lactone compound and the content of hydroxy carboxylic acids in the electrolyte solution is 20 1 mmol/kg or lower. [0016] Since hydroxy carboxylic acids have poor electrochemical oxidation resistance/reduction resistance, the cell performances deteriorate when the electrolyte solution contains a hydroxy carboxylic acid.
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