KR101195930B1 - Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same - Google Patents
Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same Download PDFInfo
- Publication number
- KR101195930B1 KR101195930B1 KR1020110002266A KR20110002266A KR101195930B1 KR 101195930 B1 KR101195930 B1 KR 101195930B1 KR 1020110002266 A KR1020110002266 A KR 1020110002266A KR 20110002266 A KR20110002266 A KR 20110002266A KR 101195930 B1 KR101195930 B1 KR 101195930B1
- Authority
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- South Korea
- Prior art keywords
- lithium secondary
- carbonate
- group
- secondary battery
- aqueous electrolyte
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 38
- -1 silane compound Chemical class 0.000 claims abstract description 31
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
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- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
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- 150000004820 halides Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical group [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Chemical group 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 2
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 claims description 2
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 claims description 2
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 claims description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 claims description 2
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 20
- 238000007086 side reaction Methods 0.000 abstract description 7
- 230000001629 suppression Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
본 발명은 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지에 관한 것이다. 본 발명의 리튬 이차전지용 비수 전해액은, 이온화 가능한 리튬염; 유기 용매; 및 하기 화학식 1로 표시되는 실란 화합물을 포함한다. 본 발명의 비수 전해액을 구비한 리튬 이차전지는 전해액의 부반응 억제 및 사이클 수명이 개선되며, 특히 고전압 전지에서 유용하게 사용될 수 있다.The present invention relates to a nonaqueous electrolyte for a lithium secondary battery and a lithium secondary battery having the same. Non-aqueous electrolyte solution for lithium secondary batteries of the present invention, the ionizable lithium salts; Organic solvents; And a silane compound represented by Formula 1 below. The lithium secondary battery having the nonaqueous electrolyte of the present invention can improve side reaction suppression and cycle life of the electrolyte, and can be particularly useful in high voltage batteries.
Description
본 발명은 실란계 첨가제를 함유하여 전해액의 분해 반응을 억제하여 사이클 수명이 개선된 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지에 관한 것이다.The present invention relates to a non-aqueous electrolyte lithium secondary battery and a lithium secondary battery having the same containing a silane-based additive to suppress the decomposition reaction of the electrolyte to improve the cycle life.
최근 에너지 저장 기술에 대한 관심이 갈수록 높아지고 있다. 휴대폰, 캠코더 및 노트북 PC, 나아가서는 전기 자동차의 에너지까지 적용 분야가 확대되면서, 이러한 전자 기기의 전원으로 사용되는 전지의 고에너지 밀도화에 대한 요구가 높아지고 있다. 리튬 이차전지는 이러한 요구를 가장 잘 충족시킬 수 있는 전지로서, 현재 이에 대한 연구가 활발히 진행되고 있다. Recently, interest in energy storage technology is increasing. As the field of application extends to the energy of mobile phones, camcorders, notebook PCs, and even electric vehicles, the demand for high energy density of batteries used as power sources for such electronic devices is increasing. Lithium secondary batteries are the ones that can best meet these demands, and researches on them are actively under way.
현재 적용되고 있는 이차전지 중에서 1990년대 초에 개발된 리튬 이차전지는 리튬이온을 흡장 및 방출할 수 있는 탄소재 등의 음극, 리튬 함유 산화물 등으로 된 양극 및 혼합 유기용매에 리튬염이 적당량 용해된 비수 전해액으로 구성되어 있다.Among the secondary batteries currently applied, lithium secondary batteries developed in the early 1990's include lithium salts dissolved in an appropriate amount of a negative electrode such as a carbon material capable of occluding and releasing lithium ions, a positive electrode made of lithium-containing oxide, and a mixed organic solvent. It consists of a nonaqueous electrolyte.
최근 리튬 이차전지의 사용이 확대되면서 고온 이나 저온 환경 등 보다 가혹한 환경에서도 우수한 성능을 유지할 수 있고 고전압으로도 안전하게 충전이 가능한 리튬 이차전지에 대한 수요가 점차 늘어나고 있다.Recently, as the use of lithium secondary batteries expands, demand for lithium secondary batteries that can maintain excellent performance even in harsher environments such as high or low temperature environments and can be safely charged even at high voltage is increasing.
그런데, 리튬 이차전지의 양극 활물질로서 사용되는 리튬 전이금속 산화물 또는 복합 산화물은 리튬 이온의 흡장 및 방출에 의해 구조적 안전성과 용량이 정해지는데, 이들의 용량은 충전 전위가 상승할수록 증가하나 이에 따라 활물질을 이루는 전이금속 등의 방출도 가속화되어 구조적 불안정이 야기될 수 있다.By the way, the lithium transition metal oxide or composite oxide used as a positive electrode active material of a lithium secondary battery has a structural safety and capacity determined by occlusion and release of lithium ions, and their capacity increases as the charging potential increases, but accordingly Release of transition metals and the like may also be accelerated, resulting in structural instability.
또한, 현재 비수 전해액은 일반적으로 에틸렌 카보네이트(EC), 디메틸 카보네이트(DMC) 등의 카보네이트계 유기 용매를 전해액 용매로 사용하고, LiPF6, LiBF4, 등의 리튬염을 전해질염으로 사용하여 제조된다. In addition, current nonaqueous electrolytes are generally prepared using carbonate-based organic solvents such as ethylene carbonate (EC) and dimethyl carbonate (DMC) as electrolyte solvents, and lithium salts such as LiPF 6 , LiBF 4 , and the like as electrolyte salts. .
그러나, 일반적으로 카보네이트계 유기 용매는 충방전 중 전극 표면에서 분해되어 전지 내에서 부반응을 일으킬 수 있으며, 에틸렌 카보네이트(EC), 디메틸 카보네이트(DMC) 또는 디에틸 카보네이트(DEC) 등 분자량이 큰 전해액 용매는 탄소계 음극에서 흑연 층간에 코인터컬레이션되어, 음극의 구조를 붕괴시킬 수 있다. 따라서, 리튬 이차 전지의 성능은 충방전이 거듭될수록 저하될 수 있다. In general, however, carbonate-based organic solvents may decompose on the surface of the electrode during charge and discharge to cause side reactions in the battery. Is co-intercalated between the graphite layers in the carbon-based negative electrode, thereby disrupting the structure of the negative electrode. Therefore, the performance of the lithium secondary battery may decrease as charging and discharging are repeated.
이는 초기 충전시 카보네이트계 유기 용매의 환원에 의해 음극 표면에 형성된 고체 전해질 계면(SEI:solid electrolyte interface)막에 의해서 해결될 수 있는 것으로 알려졌으나, 현재까지 알려진 상기의 SEI막은 음극의 지속적인 보호막으로서의 역할을 수행하기에 다소 불충분하여, 음극 표면반응이 지속되면서 전지 용량의 감소가 나타나고, 수명이 저하될 수 있다. 또한, 상기 SEI막 형성 과정 중 카보네이트계 유기 용매의 분해로 인해 CO, CO2, CH4, C2H6 등의 기체 발생 및 이로 인한 부풀음(swelling) 현상 등으로 전지의 열화가 나타나게 된다. 이 때 발생하는 분해 가스는 파우치형 또는 캔형 전지 조립체를 변형시켜 내부 단락을 유발시키며 심할 경우 전지가 발화 또는 폭발될 수 있다. 그런데 이러한 부반응은 고전압 조건에서 더욱 가속화될 수 있다.This is known to be solved by a solid electrolyte interface (SEI) film formed on the surface of the cathode by the reduction of a carbonate-based organic solvent during initial charging, but the SEI film known to date serves as a continuous protective film of the cathode. It is somewhat inadequate to carry out a decrease in battery capacity as the negative electrode surface reaction continues, and the life may be reduced. In addition, due to decomposition of the carbonate-based organic solvent during the formation of the SEI film, deterioration of the battery may occur due to generation of gases such as CO, CO 2 , CH 4 , C 2 H 6 , and swelling. The decomposition gas generated at this time deforms the pouch-type or can-type battery assembly, causing an internal short circuit, and in severe cases, the battery may ignite or explode. However, these side reactions can be further accelerated under high voltage conditions.
이러한 문제점을 해결하기 위해, 비수 전해액에 전지의 부풀음을 방지하기 위한 다양한 첨가제가 제시되었으며, 그 중에서 대표적으로 불소 등의 전자 끄는 기(electron attracting group)로 치환된 화합물들이 제안된 바 있다. In order to solve this problem, various additives have been proposed to prevent the swelling of the battery in the nonaqueous electrolyte, and among them, compounds substituted with an electron attracting group such as fluorine have been proposed.
하지만, 이러한 화합물들은 고가(高價)이며, 음극에서 쉽게 환원되는 단점이 존재하여, 아직까지 상기 문제점을 효과적으로 해결하지는 못하고 있다.However, these compounds are expensive, and there is a disadvantage in that they are easily reduced at the negative electrode, which has not yet effectively solved the problem.
따라서 본 발명이 해결하려는 과제는, 전해액의 전극 표면에서의 분해반응을 억제하고 동시에 충방전 사이클 수명도 개선할 수 있는 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지를 제공하는데 있다. Accordingly, an object of the present invention is to provide a non-aqueous electrolyte lithium secondary battery and a lithium secondary battery having the same, which can suppress the decomposition reaction on the electrode surface of the electrolyte and at the same time improve the charge / discharge cycle life.
또한, 본 발명이 해결하려는 다른 과제는, 고전압 조건에서도 전해액의 분해반응 억제 효과가 우수한 리튬 이차전지용 비수 전해액 및 이를 구비한 리튬 이차전지를 제공하는데 있다.In addition, another object of the present invention is to provide a lithium secondary battery nonaqueous electrolyte excellent in the effect of suppressing the decomposition reaction of the electrolyte even under high voltage conditions and a lithium secondary battery having the same.
상기 과제를 해결하기 위하여, 본 발명의 리튬 이차전지용 비수 전해액은, 이온화 가능한 리튬염; 유기 용매; 및 하기 화학식 1로 표시되는 실란 화합물을 포함한다:In order to solve the said subject, the nonaqueous electrolyte solution for lithium secondary batteries of this invention is ionizable lithium salt; Organic solvents; And a silane compound represented by Formula 1 below:
상기 화학식 1에서,In Formula 1,
R1, R2, R3, R4, R5, R6, R7, R8은 서로 독립적으로, R1, R2, R3, R4, R5, R6, R7, R8 are independently of each other,
수소; 할로겐; 비닐기; 알릴기; 페닐기; 벤질기; 머캅토기; 탄소수 1 내지 10인 알콕시기; 할로겐, 비닐기, 알릴기, 페닐기, 벤질기, 머캅토기, 알콕시기, 탄소수 3 내지 8인 고리형 알킬기 또는 탄소수 3 내지 8인 고리형 에폭시알킬기로 치환되거나 비치환된 탄소수 1 내지 10인 분지형 또는 직쇄형 알킬기;이다.Hydrogen; halogen; Vinyl group; Allyl group; Phenyl group; Benzyl groups; Mercapto group; An alkoxy group having 1 to 10 carbon atoms; C1-C10 branched or unsubstituted or substituted with halogen, vinyl, allyl, phenyl, benzyl, mercapto, alkoxy, cyclic alkyl groups having 3 to 8 carbon atoms or cyclic epoxyalkyl groups having 3 to 8 carbon atoms Or a straight alkyl group.
본 발명의 비수 전해액에 있어서, 상기 실란 화합물은 1-(3-머캅토)프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-클로로프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-[2-(3,4-에폭시사이클로헥실)에틸]-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-비닐-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있으나, 이에 한정되는 것은 아니다. 또한, 실란 화합물은 비수 전해액 100 중량부 대비 0.01 내지 1 중량부로 포함될 수 있다.In the nonaqueous electrolyte of the present invention, the silane compound is 1- (3-mercapto) propyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9). 1 (5,15). 1 (7,13) -octasiloxane; 1-chloropropyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9). 1 (5,15) .1 (7,13) -octasiloxane; 1- [2- (3,4-Epoxycyclohexyl) ethyl] -3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15 .1 (7,13) -octasiloxane; 1-vinyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane; Or the like may be used alone or as a mixture of two or more thereof, but is not limited thereto. In addition, the silane compound may be included in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the nonaqueous electrolyte.
본 발명의 비수 전해액에 있어서, 상기 리튬염의 음이온은 음이온은 F-, Cl-, Br-, I-, NO3 -, N(CN)2 -, BF4 -, ClO4 -, PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, CF3SO3 -, CF3CF2SO3 -, (CF3SO2)2N-, (FSO2)2N- , CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3CO2 -, CH3CO2 -, SCN-, (CF3CF2SO2)2N- 중 어느 하나일 수 있다.In the non-aqueous liquid electrolyte of the present invention, the lithium salt anion is the anion is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 - , (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, ( CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5 ) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - may be any one of -, (CF 3 CF 2 SO 2) 2 N.
본 발명의 비수 전해액에 있어서, 상기 유기용매는 에테르, 에스테르, 아미드, 선형 카보네이트, 환형 카보네이트 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.In the nonaqueous electrolyte solution of the present invention, the organic solvent may be used alone or in combination of two or more kinds of ethers, esters, amides, linear carbonates, and cyclic carbonates.
본 발명의 비수 전해액은 그 자체로 액체 전해질 또는 고분자에 함침된 겔 폴리머 전해질의 형태로 리튬 이차전지의 전해질로 사용될 수 있다.The nonaqueous electrolyte of the present invention can be used as an electrolyte of a lithium secondary battery in the form of a gel polymer electrolyte impregnated with a liquid electrolyte or a polymer per se.
본 발명의 비수 전해액은, 실란 화합물이 전극 표면에 더욱 안정한 SEI막을 형성하도록 함으로써 전해액의 전극 표면에서의 부반응을 억제하여 전지의 부풀음(swelling) 현상을 억제하는 동시에 동시에 충방전 사이클 수명도 개선할 수 있는 리튬 이차전지를 제공할 수 있다. 특히 4.2V 이상의 고전압 조건에서 전해액의 부반응 억제 및 충방전 사이클 수명 개선 효과가 우수하다.In the nonaqueous electrolyte of the present invention, the silane compound forms a more stable SEI film on the electrode surface, thereby suppressing side reactions on the electrode surface of the electrolyte, thereby suppressing swelling of the battery and at the same time improving the charge / discharge cycle life. A lithium secondary battery can be provided. In particular, it is excellent in suppressing side reaction of electrolyte solution and improving charge and discharge cycle life under high voltage condition of 4.2V or higher.
본 명세서에 첨부되는 다음의 도면들은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 안된다.
도 1은 본 발명의 실시예 및 비교예의 전지에 대해 고전압 조건에서 사이클에 따른 방전용량을 도시한 그래프이다.The following drawings, which are attached to this specification, illustrate preferred embodiments of the present invention, and together with the contents of the present invention serve to further understand the technical spirit of the present invention, the present invention is limited to the matters described in such drawings. It should not be construed as limited.
1 is a graph showing the discharge capacity according to the cycle under high voltage conditions for the batteries of the examples and comparative examples of the present invention.
이하, 본 발명을 도면을 참조하여 상세히 설명하기로 한다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Hereinafter, the present invention will be described in detail with reference to the drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
본 발명의 리튬 이차전지용 비수 전해액은, 이온화 가능한 리튬염; 유기 용매; 및 하기 화학식 1로 표시되는 실란 화합물을 포함한다.Non-aqueous electrolyte solution for lithium secondary batteries of the present invention, the ionizable lithium salts; Organic solvents; And a silane compound represented by Formula 1 below.
[화학식 1][Formula 1]
R1, R2, R3, R4, R5, R6, R7, R8은 서로 독립적으로, 수소; 할로겐; 비닐기; 알릴기; 페닐기; 벤질기; 머캅토기; 탄소수 1 내지 10인 알콕시기; 할로겐, 비닐기, 알릴기, 페닐기, 벤질기, 머캅토기, 알콕시기, 탄소수 3 내지 8인 고리형 알킬기 또는 탄소수 3 내지 8인 고리형 에폭시알킬기로 치환되거나 비치환된 탄소수 1 내지 10인 분지형 또는 직쇄형 알킬기;이다.R1, R2, R3, R4, R5, R6, R7, R8 are, independently from each other, hydrogen; halogen; Vinyl group; Allyl group; Phenyl group; Benzyl groups; Mercapto group; An alkoxy group having 1 to 10 carbon atoms; C1-C10 branched or unsubstituted or substituted with halogen, vinyl, allyl, phenyl, benzyl, mercapto, alkoxy, cyclic alkyl groups having 3 to 8 carbon atoms or cyclic epoxyalkyl groups having 3 to 8 carbon atoms Or a straight alkyl group.
상기 화학식 1에서, 할로겐, 비닐기, 알릴기, 페닐기, 벤질기, 머캅토기, 알콕시기 또는 탄소수 3 내지 8인 고리형 알킬기가 분지형 또는 직쇄형 알킬기에 치환되는 위치는 특별히 제한되지 않는다. 따라서, 분지형 또는 직쇄형 알킬 사슬의 중간 부분이거나 말단 부분일 수도 있다.In Formula 1, the position at which the halogen, vinyl group, allyl group, phenyl group, benzyl group, mercapto group, alkoxy group or cyclic alkyl group having 3 to 8 carbon atoms is substituted is not particularly limited. Thus, it may be the middle portion or the terminal portion of a branched or straight chain alkyl chain.
전술한 바와 같이, 리튬 이차전지의 음극 표면의 SEI 피막은 전해액의 부반응을 방지하는데 주요한 역할을 한다. 다만, 현재까지 알려진 유기 용매나 첨가제로 형성된 SEI막은 지속적인 성능 유지가 어려운 문제점이 있다.As described above, the SEI film on the negative electrode surface of the lithium secondary battery plays a major role in preventing side reactions of the electrolyte. However, the SEI film formed of an organic solvent or additive known to date has a problem in that it is difficult to maintain continuous performance.
하지만, 본 발명에 따른 상기 실란 화합물은 SEI막의 형성에 참여하여 막의 안정화에 기여하여 상기 문제점을 해결한다. 본 발명에 따른 실란 화합물 중 여러 작용기, 예를 들면 머캅토기 등이 전극 표면에 흡착되어 SEI막 형성에 기여하는 것으로 판단되나, 이는 추정일 뿐 이에 본 발명의 범위가 한정되는 것은 아니다. 또한, 본 발명에 따른 실란 화합물에서 실란기도 SEI 피막 형성에 참여하며, 고온 성능의 개선에 기여한다. However, the silane compound according to the present invention participates in the formation of the SEI film and contributes to the stabilization of the film to solve the above problem. It is determined that various functional groups, such as mercapto groups, among the silane compounds according to the present invention are adsorbed on the surface of the electrode to contribute to the formation of the SEI film, but this is only an estimation and the scope of the present invention is not limited thereto. In addition, in the silane compound according to the present invention, the silane also participates in SEI film formation and contributes to the improvement of high temperature performance.
특히, 본 발명의 실란 화합물은 cage구조를 갖는데, 이러한 cage 구조는 리튬 이온이 결합할 수 있는 사이트(site)를 다수 제공하게 되므로, 리튬 이온의 이동을 더욱 원활하게 함으로써 사이클 수명 및 기타 전지의 기본적인 성능의 향상을 가져오는 것으로 판단되나, 역시 이에 본 발명의 범위가 한정되는 것은 아니다.In particular, the silane compound of the present invention has a cage structure, which provides a large number of sites to which lithium ions can bind, thereby making the movement of lithium ions smoother, thereby improving cycle life and other fundamentals of batteries. Although it is determined that the performance is improved, the scope of the present invention is not limited thereto.
즉, 본 발명에 따른 상기 실란 화합물을 사용하면 안정화된 SEI 피막 형성이 가능하여 전해액의 부반응 방지 효과 및 사이클 수명이 개선된다. 특히, 전해액의 분해 반응이 더욱 활성화되는 4.2V 이상의 고전압 시스템에서도 본 발명의 상기 실란 화합물을 포함하는 비수 전해액은 우수한 전해액 분해 반응 억제 효과 및 사이클 수명 개선 효과를 발휘한다.That is, the use of the silane compound according to the present invention enables the formation of a stabilized SEI film, thereby improving the side reaction prevention effect and cycle life of the electrolyte. In particular, even in a high voltage system of 4.2 V or more in which the decomposition reaction of the electrolyte is further activated, the nonaqueous electrolyte containing the silane compound of the present invention exhibits an excellent effect of inhibiting the decomposition reaction of the electrolyte and improving the cycle life.
상기 화학식 1로 표시되는 실란 화합물의 구체적인 예시로는 1-(3-머캅토)프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-클로로프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-[2-(3,4-에폭시사이클로헥실)에틸]-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 및 1-비닐-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 들 수 있으나, 이에 한정되는 것은 아니다.Specific examples of the silane compound represented by Formula 1 include 1- (3-mercapto) propyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane; 1-chloropropyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9). 1 (5,15) .1 (7,13) -octasiloxane; 1- [2- (3,4-Epoxycyclohexyl) ethyl] -3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15 .1 (7,13) -octasiloxane; And 1-vinyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane It may be any one selected from the group consisting of or a mixture of two or more thereof, but is not limited thereto.
본 발명에 따른 상기 실란 화합물은 비수 전해액 100 중량부 대비 0.01 내지 1 중량부로 포함되는 것이 바람직하다. 함량이 0.01 중량부 미만이면 SEI막 표면에서 전해액 유기용매의 분해 억제 기능이 충분하지 못할 수 있고, 1 중량부 초과이면 일반적인 전해액에 대한 용해도를 초과할 수 있으므로 용해되지 못한 일부 실란 화합물이 전지의 저항증가의 원인이 될 수도 있다. 이러한 측면에서, 본 발명에 따른 실란 화합물은 보다 바람직하게는 0.05 중량부 내지 1 중량부, 가장 바람직하게는 0.1 중량부 내지 1 중량부로 비수 전해액에 포함될 수 있다.The silane compound according to the present invention is preferably included in 0.01 to 1 parts by weight relative to 100 parts by weight of the nonaqueous electrolyte. If the content is less than 0.01 parts by weight of the SEI membrane surface may not be sufficient to inhibit the decomposition of the electrolyte organic solvent, and if more than 1 part by weight may exceed the solubility in the general electrolyte solution, some of the silane compound that is not dissolved in the battery resistance It may also cause an increase. In this aspect, the silane compound according to the present invention may be included in the non-aqueous electrolyte more preferably 0.05 parts by weight to 1 part by weight, most preferably 0.1 parts by weight to 1 parts by weight.
본 발명의 비수 전해액에 전해질로서 포함되는 리튬염은 리튬 이차전지용 전해액에 통상적으로 사용되는 것들이 제한 없이 사용될 수 있으며, 예를 들어 상기 리튬염의 음이온으로는 F-, Cl-, Br-, I-, NO3 -, N(CN)2 -, BF4 -, ClO4 -, PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, CF3SO3 -, CF3CF2SO3 -, (CF3SO2)2N-, (FSO2)2N- , CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3CO2 -, CH3CO2 -, SCN- 및 (CF3CF2SO2)2N-로 이루어진 군에서 선택된 어느 하나일 수 있다.The lithium salt contained as an electrolyte in a non-aqueous liquid electrolyte of the present invention can be used without limitation, those which are commonly used in a lithium secondary battery electrolyte, such as the lithium salt, the anion is F -, Cl -, Br -, I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - and (CF 3 CF 2 SO 2 ) 2 N - .
전술한 본 발명의 비수 전해액에 포함되는 유기 용매로는 리튬 이차전지용 전해액에 통상적으로 사용되는 것들을 제한 없이 사용할 수 있으며, 예를 들면 에테르, 에스테르, 아미드, 선형 카보네이트, 환형 카보네이트 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다.As the organic solvent included in the nonaqueous electrolyte of the present invention described above, those conventionally used in the lithium secondary battery electrolyte may be used without limitation, and for example, ethers, esters, amides, linear carbonates, cyclic carbonates, and the like may be used alone or independently. It can mix and use 2 or more types.
그 중에서 대표적으로는 환형 카보네이트, 선형 카보네이트, 또는 이들의 혼합물인 카보네이트 화합물을 포함할 수 있다. 상기 환형 카보네이트 화합물의 구체적인 예로는 에틸렌 카보네이트(ethylene carbonate, EC), 프로필렌 카보네이트(propylene carbonate, PC), 1,2-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 비닐렌 카보네이트 및 이들의 할로겐화물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물이 있다. 또한 상기 선형 카보네이트 화합물의 구체적인 예로는 디메틸 카보네이트(dimethyl carbonate, DMC), 디에틸 카보네이트(diethyl carbonate, DEC), 디프로필 카보네이트, 에틸메틸 카보네이트(EMC), 메틸프로필 카보네이트 및 에틸프로필 카보네이트 로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물 등이 대표적으로 사용될 수 있으나, 이에 한정되는 것은 아니다.Among them, a carbonate compound which is typically a cyclic carbonate, a linear carbonate, or a mixture thereof may be included. Specific examples of the cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, and any one selected from the group consisting of halides thereof or mixtures of two or more thereof. Specific examples of the linear carbonate compounds include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate. Any one selected or a mixture of two or more thereof may be representatively used, but is not limited thereto.
특히, 상기 카보네이트계 유기용매 중 환형 카보네이트인 에틸렌 카보네이트 및 프로필렌 카보네이트는 고점도의 유기용매로서 유전율이 높아 전해질 내의 리튬염을 잘 해리시키므로 바람직하게 사용될 수 있으며, 이러한 환형 카보네이트에 디메틸 카보네이트 및 디에틸 카보네이트와 같은 저점도, 저유전율 선형 카보네이트를 적당한 비율로 혼합하여 사용하면 높은 전기 전도율을 갖는 전해액을 만들 수 있어 더욱 바람직하게 사용될 수 있다.In particular, ethylene carbonate and propylene carbonate, which are cyclic carbonates among the carbonate-based organic solvents, are highly viscous organic solvents, and thus may be preferably used because they dissociate lithium salts in the electrolyte well, such as dimethyl carbonate and diethyl carbonate. When the same low viscosity, low dielectric constant linear carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be made, and thus it can be used more preferably.
또한, 상기 유기 용매 중 에테르로는 디메틸 에테르, 디에틸 에테르, 디프로필 에테르, 메틸에틸 에테르, 메틸프로필 에테르 및 에틸프로필 에테르로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.As the ether in the organic solvent, any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether or a mixture of two or more thereof may be used , But is not limited thereto.
그리고 상기 유기 용매 중 에스테르로는 메틸 아세테이트, 에틸 아세테이트, 프로필 아세테이트, 메틸 프로피오네이트, 에틸 프로피오네이트, γ-부티로락톤, γ-발레로락톤, γ-카프로락톤, σ-발레로락톤 및 ε-카프로락톤으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.Examples of the ester in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate,? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone, ε-caprolactone, or a mixture of two or more thereof, but the present invention is not limited thereto.
전술한 본 발명의 리튬 이차전지용 비수 전해액은 양극, 음극 및 양극과 음극 사이에 개재된 세퍼레이터로 이루어진 전극 구조체에 주입하여 리튬 이차전지로 제조된다. 전극 구조체를 이루는 양극, 음극 및 세퍼레이터는 리튬 이차전지 제조에 통상적으로 사용되던 것들이 모두 사용될 수 있다.The non-aqueous electrolyte solution for a lithium secondary battery of the present invention described above is manufactured into a lithium secondary battery by injecting an electrode structure composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode. As the positive electrode, the negative electrode, and the separator constituting the electrode structure, all those conventionally used for manufacturing a lithium secondary battery may be used.
구체적인 예로서, 양극 활물질로는 리튬함유 전이금속 산화물이 바람직하게 사용될 수 있으며, 예를 들면 LixCoO2(0.5<x<1.3), LixNiO2(0.5<x<1.3), LixMnO2(0.5<x<1.3), LixMn2O4(0.5<x<1.3), Lix(NiaCobMnc)O2(0.5<x<1.3, 0<a<1, 0<b<1, 0<c<1, a+b+c=1), LixNi1 -yCoyO2(0.5<x<1.3, 0<y<1), LixCo1 -yMnyO2(0.5<x<1.3, 0≤y<1), LixNi1 -yMnyO2(0.5<x<1.3, O≤y<1), Lix(NiaCobMnc)O4(0.5<x<1.3, 0<a<2, 0<b<2, 0<c<2, a+b+c=2), LixMn2 -zNizO4(0.5<x<1.3, 0<z<2), LixMn2 -zCozO4(0.5<x<1.3, 0<z<2), LixCoPO4(0.5<x<1.3) 및 LixFePO4(0.5<x<1.3)로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 사용할 수 있으며, 상기 리튬함유 전이금속 산화물은 알루미늄(Al) 등의 금속이나 금속산화물로 코팅될 수도 있다. 또한, 상기 리튬함유 전이금속 산화물(oxide) 외에 황화물(sulfide), 셀렌화물(selenide) 및 할로겐화물(halide) 등도 사용될 수 있다. As a specific example, a lithium-containing transition metal oxide may be preferably used as the cathode active material. For example, Li x CoO 2 (0.5 <x <1.3), Li x NiO 2 (0.5 <x <1.3), and Li x MnO 2 (0.5 <x <1.3), Li x Mn 2 O 4 (0.5 <x <1.3), Li x (Ni a Co b Mn c ) O 2 (0.5 <x <1.3, 0 <a <1, 0 < b <1, 0 <c <1, a + b + c = 1), Li x Ni 1 -y Co y O 2 (0.5 <x <1.3, 0 <y <1), Li x Co 1 -y Mn y O 2 (0.5 <x <1.3, 0 ≦ y <1), Li x Ni 1- y Mn y O 2 (0.5 <x <1.3, O ≦ y <1), Li x (Ni a Co b Mn c ) O 4 (0.5 <x <1.3, 0 <a <2, 0 <b <2, 0 <c <2, a + b + c = 2), Li x Mn 2 -z Ni z O 4 (0.5 < x <1.3, 0 <z <2), Li x Mn 2 -z Co z O 4 (0.5 <x <1.3, 0 <z <2), Li x CoPO 4 (0.5 <x <1.3) and Li x FePO 4 (0.5 <x <1.3) may be used any one selected from the group consisting of or a mixture of two or more thereof, and the lithium-containing transition metal oxide may be coated with a metal or metal oxide such as aluminum (Al). . In addition to the lithium-containing transition metal oxide, sulfide, selenide, halide, and the like may also be used.
음극 활물질로는 통상적으로 리튬이온이 흡장 및 방출될 수 있는 탄소재, 리튬금속, 규소 또는 주석 등을 사용할 수 있으며, 리튬에 대한 전위가 2V 미만인 TiO2, SnO2와 같은 금속 산화물도 가능하다. 바람직하게는 탄소재를 사용할 수 있는데, 탄소재로는 저결정 탄소 및 고결정성 탄소 등이 모두 사용될 수 있다. 저결정성 탄소로는 연화탄소(soft carbon) 및 경화탄소(hard carbon)가 대표적이며, 고결정성 탄소로는 천연 흑연, 키시흑연(Kish graphite), 열분해 탄소(pyrolytic carbon), 액정 피치계 탄소섬유(mesophase pitch based carbon fiber), 탄소 미소구체(meso-carbon microbeads), 액정피치(Mesophase pitches) 및 석유와 석탄계 코크스(petroleum or coal tar pitch derived cokes) 등의 고온 소성탄소가 대표적이다. As the negative electrode active material, a carbon material, lithium metal, silicon, tin, or the like, which can normally occlude and release lithium ions, may be used, and a metal oxide such as TiO 2 and SnO 2 having a potential of less than 2 V may be used. Preferably, a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used. Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch-based carbon fiber. High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
양극 및/또는 음극은 바인더를 포함할 수 있으며, 바인더로는 비닐리덴플루오라이드-헥사플루오로프로필렌 코폴리머(PVDF-co-HFP), 폴리비닐리덴플루오라이드(polyvinylidenefluoride), 폴리아크릴로니트릴(polyacrylonitrile), 폴리메틸메타크릴레이트(polymethylmethacrylate) 등, 다양한 종류의 바인더 고분자가 사용될 수 있다. The positive electrode and / or the negative electrode may include a binder, and the binder may include vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile ), Various types of binder polymers such as polymethylmethacrylate may be used.
또한, 세퍼레이터로는 종래에 세퍼레이터로 사용된 통상적인 다공성 고분자 필름, 예를 들어 에틸렌 단독중합체, 프로필렌 단독중합체, 에틸렌/부텐 공중합체, 에틸렌/헥센 공중합체 및 에틸렌/메타크릴레이트 공중합체 등과 같은 폴리올레핀계 고분자로 제조한 다공성 고분자 필름을 단독으로 또는 이들을 적층하여 사용할 수 있으며, 또는 통상적인 다공성 부직포, 예를 들어 고융점의 유리 섬유, 폴리에틸렌테레프탈레이트 섬유 등으로 된 부직포를 사용할 수 있으나, 이에 한정되는 것은 아니다.In addition, as the separator, conventional porous polymer films conventionally used as separators, for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer, etc. The porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
본 발명의 리튬 이차전지의 외형은 특별한 제한이 없으나, 캔을 사용한 원통형, 각형, 파우치(pouch)형 또는 코인(coin)형 등이 될 수 있다.The external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.
Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예Example 1 One
<비수 전해액의 제조><Production of Nonaqueous Electrolyte>
에틸렌 카보네이트: 에틸메틸 카보네이트 = 1 : 2(부피비)의 조성을 가지는 1M LiPF6 용액을 전해액으로 사용하였고, 상기 전해액 100 중량부 대비 1-비닐-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산 0.1 중량부를 첨가하였다.Ethylene carbonate: Ethyl methyl carbonate = 1 M LiPF 6 solution having a composition of 1: 2 (volume ratio) was used as the electrolyte, 1-vinyl-3,5,7,9,1,13,15- with respect to 100 parts by weight of the electrolyte 0.1 part by weight of isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane was added.
<전지의 제조><Manufacture of battery>
양극 활물질로 LiCoO2, 바인더로서 폴리비닐리덴 플루오라이드(PVdF) 및 도전재로 카본을 93:4:4의 중량비로 혼합한 후, N-메틸-2-피롤리돈에 분산시켜 양극 슬러리를 제조하고, 상기 슬러리를 알루미늄 집전체에 코팅한 후 건조 및 압연하여 양극을 제조하였다.A positive electrode slurry was prepared by mixing LiCoO 2 as a positive electrode active material, polyvinylidene fluoride (PVdF) as a binder, and carbon at a weight ratio of 93: 4: 4 with a conductive material, and then dispersing it in N-methyl-2-pyrrolidone. The slurry was coated on an aluminum current collector and then dried and rolled to prepare a positive electrode.
또한, 음극 활물질로 천연 흑연, 바인더로서 스티렌-부타디엔 고무 및 증점제로 카르복시메틸 셀룰로오스를 96:2:2의 중량비로 혼합한 후, 물에 분산시켜 음극 슬러리를 제조하고, 상기 슬러리를 구리 집전체에 코팅한 후 건조 및 압연하여 음극을 제조하였다.Further, natural graphite as a negative electrode active material, styrene-butadiene rubber as a binder and carboxymethyl cellulose as a thickener are mixed in a weight ratio of 96: 2: 2, and then dispersed in water to prepare a negative electrode slurry, and the slurry is coated on a copper current collector. After coating, it was dried and rolled to prepare a negative electrode.
이후, 상기 제조된 양극과 음극을 PE 분리막과 함께 통상적인 방법으로 코인형 전지를 제작한 후, 상기 전해액을 주액하여 전지 제조를 완성하였다.Thereafter, a coin-type battery was manufactured by the conventional method using the prepared positive electrode and the negative electrode together with the PE separator, followed by pouring the electrolyte solution to complete the battery manufacturing.
실시예Example 2 2
실란화합물로서 1-(3-머캅토)프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산(화학식 1에서, R1~R7: , R8: -(CH2)3-SH) 0.1 중량부를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 비수전해액 및 전지를 제조하였다.1- (3-mercapto) propyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 ( 7,13) -octasiloxane (In Formula 1, R1-R7: , R8:-(CH 2 ) 3 -SH) A non-aqueous electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.1 part by weight was used.
실시예Example 3 3
실란화합물로서 1-[2-(3,4-에폭시사이클로헥실)에틸]-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산 0.1 중량부를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 비수전해액 및 전지를 제조하였다.1- [2- (3,4-epoxycyclohexyl) ethyl] -3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 ( 5,15). A non-aqueous electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.1 part by weight of 1 (7,13) -octasiloxane was used.
실시예Example 4 4
실란화합물로서 1-클로로프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산 0.1 중량부를 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 비수전해액 및 전지를 제조하였다.
1-chloropropyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13)-as silane compound A nonaqueous electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.1 part by weight of octasiloxane was used.
비교예Comparative example
실란 화합물을 첨가하지 않은 것을 제외하고는, 실시예1과 동일한 방법으로 전해액 및 전지를 제조하였다.
An electrolyte solution and a battery were manufactured in the same manner as in Example 1, except that the silane compound was not added.
시험예Test Example : 고전압 조건에서 : Under high voltage 충방전Charging and discharging 사이클 수명 측정 Cycle life measurement
실시예 및 비교예에서 제조된 코인형 전지를 4.35V~3.0V cut off 전압 영역 기준으로 0.5C 충전 및 0.5C 방전 조건으로 충방전 사이클 시험을 수행하였고, 그 결과를 도 1에 나타내었다. The coin-type battery manufactured in Examples and Comparative Examples was subjected to a charge and discharge cycle test under 0.5C charge and 0.5C discharge conditions based on the 4.35V to 3.0V cut off voltage range, and the results are shown in FIG. 1.
도 1에 나타난 바와 같이, 본 발명에 따른 실란 화합물을 첨가한 실시예들은 고전압 조건에서도 사이클이 증가해도 용량 저하가 적어 실란 화합물을 첨가하지 않은 비교예보다 사이클 수명이 현저히 개선되는 효과가 있음을 확인할 수 있다. As shown in FIG. 1, the examples in which the silane compound was added according to the present invention had a decrease in capacity even when the cycle was increased even under high voltage, resulting in a significantly improved cycle life compared to the comparative example without the addition of the silane compound. Can be.
Claims (10)
유기 용매; 및
하기 화학식 1로 표시되는 실란 화합물을 포함하는 리튬 이차전지용 비수 전해액:
[화학식 1]
상기 화학식 1에서,
R1, R2, R3, R4, R5, R6, R7, R8은 서로 독립적으로, 수소; 할로겐; 비닐기; 알릴기; 페닐기; 벤질기; 머캅토기; 탄소수 1 내지 10인 알콕시기; 할로겐, 비닐기, 알릴기, 페닐기, 벤질기, 머캅토기, 알콕시기, 탄소수 3 내지 8인 고리형 알킬기 또는 탄소수 3 내지 8인 고리형 에폭시알킬기로 치환되거나 비치환된 탄소수 1 내지 10인 분지형 또는 직쇄형 알킬기;이다.Ionizable lithium salts;
Organic solvents; And
A nonaqueous electrolyte solution for a lithium secondary battery comprising a silane compound represented by Formula 1 below:
[Formula 1]
In Chemical Formula 1,
R1, R2, R3, R4, R5, R6, R7, R8 are, independently from each other, hydrogen; halogen; Vinyl group; Allyl group; Phenyl group; Benzyl groups; Mercapto group; An alkoxy group having 1 to 10 carbon atoms; C1-C10 branched or unsubstituted or substituted with halogen, vinyl, allyl, phenyl, benzyl, mercapto, alkoxy, cyclic alkyl groups having 3 to 8 carbon atoms or cyclic epoxyalkyl groups having 3 to 8 carbon atoms Or a straight alkyl group.
상기 실란 화합물은 1-(3-머캅토)프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-클로로프로필-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 1-[2-(3,4-에폭시사이클로헥실)에틸]-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산; 및 1-비닐-3,5,7,9,1,13,15-이소부틸펜타사이클로-9.5.1.1(3,9).1(5,15).1(7,13)-옥타실록산으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 1,
The silane compound is 1- (3-mercapto) propyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane; 1-chloropropyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9). 1 (5,15) .1 (7,13) -octasiloxane; 1- [2- (3,4-Epoxycyclohexyl) ethyl] -3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15 .1 (7,13) -octasiloxane; And 1-vinyl-3,5,7,9,1,13,15-isobutylpentacyclo-9.5.1.1 (3,9) .1 (5,15) .1 (7,13) -octasiloxane Non-aqueous electrolyte solution for lithium secondary batteries, characterized in that any one or a mixture of two or more selected from the group consisting of.
상기 실란 화합물은 비수 전해액 100 중량부 대비 0.01 내지 1 중량부로 포함되는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 1,
The silane compound is a non-aqueous electrolyte lithium secondary battery, characterized in that it comprises 0.01 to 1 part by weight relative to 100 parts by weight of the non-aqueous electrolyte.
상기 리튬염의 음이온은 F-, Cl-, Br-, I-, NO3 -, N(CN)2 -, BF4 -, ClO4 -, PF6 -, (CF3)2PF4 -, (CF3)3PF3 -, (CF3)4PF2 -, (CF3)5PF-, (CF3)6P-, CF3SO3 -, CF3CF2SO3 -, (CF3SO2)2N-, (FSO2)2N- , CF3CF2(CF3)2CO-, (CF3SO2)2CH-, (SF5)3C-, (CF3SO2)3C-, CF3(CF2)7SO3 -, CF3CO2 -, CH3CO2 -, SCN- 및 (CF3CF2SO2)2N-로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 1,
The lithium salt of the anion is F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, ( CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, ( FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2 ) 3 C -, CF 3 ( CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN - and (CF 3 CF 2 SO 2 ) 2 N -Non- aqueous electrolyte solution for a lithium secondary battery, characterized in that any one selected from the group consisting of.
상기 유기 용매는 에테르, 에스테르, 아미드, 선형 카보네이트 및 환형 카보네이트로 이루어진 군으로부터 선택된 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 1,
The organic solvent is any one selected from the group consisting of ethers, esters, amides, linear carbonates and cyclic carbonates, or a mixture of two or more thereof.
상기 환형 카보네이트는 에틸렌 카보네이트, 프로필렌 카보네이트, 1,2-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 비닐렌 카보네이트 및 이들의 할로겐화물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 5,
The cyclic carbonates are ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and their halides Non-aqueous electrolyte solution for a lithium secondary battery comprising any one selected from the group consisting of or a mixture of two or more thereof.
상기 선형 카보네이트는 디메틸 카보네이트, 디에틸 카보네이트, 디프로필 카보네이트, 에틸메틸 카보네이트, 메틸프로필 카보네이트 및 에틸프로필카보네이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 5,
The linear carbonate is lithium secondary, characterized in that it contains any one or a mixture of two or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate and ethylpropyl carbonate Non-aqueous electrolyte solution for batteries.
상기 에테르는 디메틸 에테르, 디에틸 에테르, 디프로필 에테르, 메틸에틸 에테르, 메틸프로필 에테르 및 에틸프로필 에테르로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 5,
The ether is any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or a mixture of two or more thereof. Nonaqueous electrolyte.
상기 에스테르는 메틸 아세테이트, 에틸 아세테이트, 프로필 아세테이트, 메틸 프로피오네이트, 에틸 프로피오네이트, γ-부티로락톤, γ-발레로락톤, γ-카프로락톤, σ-발레로락톤 및 ε-카프로락톤으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 리튬 이차전지용 비수 전해액.The method of claim 5,
The esters are methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone and ε-caprolactone Non-aqueous electrolyte solution for lithium secondary batteries comprising any one selected from the group consisting of or a mixture of two or more thereof.
상기 비수 전해액은 제1항 내지 제9항 중 어느 한 항의 리튬 이차전지용 비수 전해액인 것을 특징으로 하는 리튬 이차전지. In a lithium secondary battery comprising a negative electrode, a positive electrode and a nonaqueous electrolyte,
The nonaqueous electrolyte is a lithium secondary battery, characterized in that the nonaqueous electrolyte for lithium secondary battery of any one of claims 1 to 9.
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