JP4488994B2 - リチウムイオン二次電池用電解液及びこれを含むリチウムイオン二次電池 - Google Patents
リチウムイオン二次電池用電解液及びこれを含むリチウムイオン二次電池 Download PDFInfo
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- JP4488994B2 JP4488994B2 JP2005284002A JP2005284002A JP4488994B2 JP 4488994 B2 JP4488994 B2 JP 4488994B2 JP 2005284002 A JP2005284002 A JP 2005284002A JP 2005284002 A JP2005284002 A JP 2005284002A JP 4488994 B2 JP4488994 B2 JP 4488994B2
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- secondary battery
- ion secondary
- lithium ion
- carbonate
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 53
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 53
- 239000008151 electrolyte solution Substances 0.000 title claims description 39
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 48
- 239000003792 electrolyte Substances 0.000 claims description 45
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 24
- 239000012190 activator Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- -1 acyclic carbonates Chemical class 0.000 claims description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 239000007774 positive electrode material Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 7
- 238000009831 deintercalation Methods 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 7
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002015 acyclic group Chemical group 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000004292 cyclic ethers Chemical class 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 3
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 3
- 229910010090 LiAlO 4 Inorganic materials 0.000 claims description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013372 LiC 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- 229910013131 LiN Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- GSURLQOINUQIIH-UHFFFAOYSA-N triheptyl phosphate Chemical compound CCCCCCCOP(=O)(OCCCCCCC)OCCCCCCC GSURLQOINUQIIH-UHFFFAOYSA-N 0.000 claims description 3
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 claims description 3
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000001491 aromatic compounds Chemical group 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 3
- 239000013543 active substance Substances 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 15
- 238000009736 wetting Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZYKOICDLSSOLAN-UHFFFAOYSA-N diheptyl carbonate Chemical compound CCCCCCCOC(=O)OCCCCCCC ZYKOICDLSSOLAN-UHFFFAOYSA-N 0.000 description 1
- OKQDSOXFNBWWJL-UHFFFAOYSA-N dihexyl carbonate Chemical compound CCCCCCOC(=O)OCCCCCC OKQDSOXFNBWWJL-UHFFFAOYSA-N 0.000 description 1
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 1
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- UWPBHWLIAMQGLC-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC.CCCCOP(=O)(OCCCC)OCCCC UWPBHWLIAMQGLC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
人工黒鉛負極活物質をカルボキシメチルセルロース水溶液に懸濁させ,スチレン−ブタジエンゴムバインダーを添加して負極活物質スラリーを製造した。このスラリーを厚さ10μmの銅ホイルにコーティングし,乾燥,圧延して負極を製造した。
ジ−n−ブチルカーボネートを3質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートを5質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートを7質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ガンマブチロラクトンを50体積%,ジ−n−ブチルカーボネートを5質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ガンマブチロラクトンを70体積%,ジ−n−ブチルカーボネートを10質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートの代わりに,トリブチルホスフェートを3質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートの代わりに,トリオクチルホスフェートを3質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
電解液にガンマブチロラクトン及び添加剤(湿潤性活性剤)であるジ−n−ブチルカーボネートを添加しないことを除いては,上記の実施例1と同一の構成で実施した。
ガンマブチロラクトンを添加していない電解液にジ−n−ブチルカーボネートを5質量%添加したことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートを添加しないことを除いては,上記の実施例1と同一の構成で実施した。
ジ−n−ブチルカーボネートを添加しない電解液にガンマブチロラクトンを60体積%添加したことを除いては,上記の実施例1と同一の構成で実施した。
各サイクルの容量維持率(%)=[(各サイクルの放電容量)/(1サイクル目の放電容量)]*100
12 電極組立体
13 正極
14 セパレータ
15 負極
16 正極タブ
17 負極タブ
20 キャップ組立体
30 電極端子
40 キャッププレート
42 電解液注入孔
43 栓
46 チューブ型ガスケット
50 絶縁プレート
60 ターミナルプレート
70 絶縁ケース
Claims (18)
- リチウム塩と,
非水性有機溶媒と,
ガンマブチロラクトンと,
湿潤性活性剤として,下記の化学式2のトリアルキルホスフェートと,
を含み,
前記ガンマブチロラクトンは,前記非水性有機溶媒の全体体積に対し,1体積%〜50体積%であり,
前記化学式2のトリアルキルホスフェートは,電解液の全体質量に対し,1〜10質量%であることを特徴とする,リチウムイオン二次電池用電解液。
- 前記トリアルキルホスフェートは,トリブチルホスフェート,トリペンチルホスフェート,トリヘキシルホスフェート,トリヘプチルホスフェート及びトリオクチルホスフェートからなる群より選択される少なくとも1つであることを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 前記湿潤性活性剤は,電解液全体質量に対し,1.0質量%〜5.0質量%であることを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 前記ガンマブチロラクトンは,前記非水性有機溶媒の全体体積に対し,30体積%〜50体積%であることを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 前記非水性有機溶媒は,環状カーボネート,非環状カーボネート,脂肪族カルボキシル酸エステル,非環状エーテル及び環状エーテルからなる群から選択される1つ,または,2つ以上が混合したものであることを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 前記環状カーボネートは,エチレンカーボネート,プロピレンカーボネート,ブチレンカーボネート及びビニレンカーボネートからなる群より選択される1つ以上のカーボネートであることを特徴とする,請求項5記載のリチウムイオン二次電池用電解液。
- 前記非環状カーボネートは,ジメチルカーボネート,ジエチルカーボネート,エチルメチルカーボネート,メチルプロピルカーボネート,エチルプロピルカーボネート,ジプロピルカーボネート及びメチルエチルカーボネートからなる群より選択される1つ以上のカーボネートであることを特徴とする,請求項5記載のリチウムイオン二次電池用電解液。
- 前記脂肪族カルボキシル酸エステルは,メチルホスフェート,メチルアセテート,メチルプロピオネート及びエチルプロピオネートからなる群より選択される1つ以上のエステルであることを特徴とする,請求項5記載のリチウムイオン二次電池用電解液。
- 前記非環状エーテルは,1,2−ジメトキシエタン,1,2−ジエトキシエタン及びエトキシメトキシエタンからなる群より選択される1つ以上のエーテルであることを特徴とする,請求項5記載のリチウムイオン二次電池用電解液。
- 前記環状エーテルは,テトラヒドロフラン及び2−メチルテトラヒドラフランからなる群より選択される1つ以上のエーテルであることを特徴とする,請求項5記載のリチウムイオン二次電池用電解液。
- 前記非水性有機溶媒は,芳香族炭化水素系有機溶媒を更に含むことを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 前記芳香族炭化水素系有機溶媒は,下記の化学式3の芳香族化合物であることを特徴とする,請求項11記載のリチウムイオン二次電池用電解液。
- 前記芳香族炭化水素系有機溶媒は,ベンゼン,フルオロベンゼン,クロロベンゼン,ブロモベンゼン,トルエン,キシレン,メシチレンからなる群より選択される少なくとも1つ,または,2つ以上が混合した溶媒であることを特徴とする,請求項12記載のリチウムイオン二次電池用電解液。
- 前記非水性有機溶媒と前記芳香族炭化水素系有機溶媒は,1:1〜30:1の体積比で混合されることを特徴とする,請求項11記載のリチウムイオン二次電池用電解液。
- 前記リチウム塩は,LiPF6,LiBF4,LiSbF6,LiAsF6,LiClO4,LiCF3SO3,Li(CF3SO2)2N,LiC4F9SO3,LiAlO4,LiAlCl4,LiN(CxF2x+1SO2)(CyF2y+1SO2)(ここで,x及びyは自然数である),LiCl及びLiIの中から選択される1つ,または,2つ以上であることを特徴とする,請求項1記載のリチウムイオン二次電池用電解液。
- 請求項1〜15のいずれか1項に記載のリチウムイオン二次電池用電解液と,リチウムイオンを可逆的にインターカレート/デインターカレートできる正極活物質を含む正極と,リチウムイオンを可逆的にインターカレート/デインターカレートできる負極活物質を含む負極と,前記正極と負極との間に配置されるセパレータとを含むことを特徴とする,リチウムイオン二次電池。
- 前記正極活物質は,リチウム系複合酸化物(lithiated intercalation oxide)であることを特徴とする,請求項16記載のリチウムイオン二次電池。
- 前記負極活物質は,結晶性炭素,非晶質炭素,炭素複合体及び金属リチウムからなる群より選択されるものであることを特徴とする,請求項16記載のリチウムイオン二次電池。
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KR20060045257A (ko) * | 2004-11-12 | 2006-05-17 | 주식회사 나래나노텍 | 알킬포스페이트계 화합물이 첨가된 리튬폴리머전지용 겔폴리머전해질 |
KR101191636B1 (ko) * | 2005-02-28 | 2012-10-18 | 삼성에스디아이 주식회사 | 리튬 전지용 전해질 및 그를 포함하는 리튬 전지 |
JP5007507B2 (ja) * | 2006-01-31 | 2012-08-22 | ソニー株式会社 | 二次電池用非水電解質組成物及び非水電解質二次電池 |
JP5007506B2 (ja) * | 2006-01-31 | 2012-08-22 | ソニー株式会社 | 二次電池用非水電解質組成物及びこれを用いた非水電解質二次電池 |
JP5007508B2 (ja) * | 2006-01-31 | 2012-08-22 | ソニー株式会社 | 二次電池用非水電解質組成物及び非水電解質二次電池 |
CN101202359B (zh) * | 2006-12-14 | 2010-05-19 | 上海比亚迪有限公司 | 一种添加剂组合物以及含该添加剂组合物的电解液和锂离子二次电池 |
US8795903B2 (en) * | 2008-08-19 | 2014-08-05 | California Institute Of Technology | Lithium-ion electrolytes containing flame retardant additives for increased safety characteristics |
JP5306749B2 (ja) * | 2008-09-11 | 2013-10-02 | 国立大学法人静岡大学 | 電気化学デバイス |
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CN102315483A (zh) * | 2011-09-30 | 2012-01-11 | 湖南大学 | 一种新型多功能电解液 |
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CN111224161B (zh) * | 2018-11-26 | 2021-06-15 | 中国科学院大连化学物理研究所 | 一种含有添加剂的电解液提高锂离子电池低温使用性能的方法 |
CN111313118B (zh) * | 2020-04-13 | 2021-07-06 | 东方醒狮储能电池有限公司 | 一种锂离子电池的化成方法 |
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KR20060029747A (ko) | 2006-04-07 |
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US20060073391A1 (en) | 2006-04-06 |
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