JP5159268B2 - 非水電解質電池 - Google Patents
非水電解質電池 Download PDFInfo
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- JP5159268B2 JP5159268B2 JP2007301653A JP2007301653A JP5159268B2 JP 5159268 B2 JP5159268 B2 JP 5159268B2 JP 2007301653 A JP2007301653 A JP 2007301653A JP 2007301653 A JP2007301653 A JP 2007301653A JP 5159268 B2 JP5159268 B2 JP 5159268B2
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 63
- 229910052744 lithium Inorganic materials 0.000 claims description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 49
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 33
- 239000007773 negative electrode material Substances 0.000 claims description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims description 27
- -1 cyclic carbonic acid ester Chemical class 0.000 claims description 26
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 26
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- 150000004651 carbonic acid esters Chemical class 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 36
- 238000002474 experimental method Methods 0.000 description 28
- 150000005676 cyclic carbonates Chemical class 0.000 description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 25
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 23
- 229910013870 LiPF 6 Inorganic materials 0.000 description 22
- 239000000203 mixture Substances 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000011149 active material Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 238000003780 insertion Methods 0.000 description 6
- 230000037431 insertion Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000005678 chain carbonates Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910012425 Li3Fe2 (PO4)3 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910010701 LiFeP Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910016243 LiMn1.5Ni0.45Mg0.05O4 Inorganic materials 0.000 description 1
- 229910014918 LiMn7/8Fe1/8PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FKQOMXQAEKRXDM-UHFFFAOYSA-N [Li].[As] Chemical compound [Li].[As] FKQOMXQAEKRXDM-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
正極活物質である六方晶岩塩型結晶構造を有するリチウム遷移金属複合酸化物(LiNi1/6Mn1/6Co2/3O2)粉末90質量部、導電材であるアセチレンブラック5質量部及び結着剤であるポリフッ化ビニリデン(PVdF)5質量部を含有し、N−メチルピロリドン(NMP)を溶剤とする正極スラリーを正極集電体(アルミニウム製、厚み20μm)に、片面の電極合剤量が10mg/cm2(集電体含まず)になるように塗布した後、乾燥し、両面の電極厚みが90μm(集電体含む)となるようにプレスすることにより正極を作製した。
完成後の電池について、温度25℃にて、充電電流450mA、充電電圧2.5V、充電時間3時間の定電流定電圧充電を行った後、放電電流450mA、放電終止電圧1.0Vの放電を行い、このときの放電容量を「電池容量(mAh)」として記録した。電池は、引き続く試験に備えるため、再び、充電電流450mA、充電電圧2.5V、充電時間3時間の定電流定電圧充電を温度25℃にて行い、SOC100%に調整した。
出力特性試験に供試する電池は、−30℃の温度環境下に5時間以上放置した後、種々の放電電流値で各30秒の放電を行った。ここで、放電電流値は900mA、1350mA、1800mA及び2250mAを採用し、この順番で試験を行った。なお、それぞれの放電後には、1時間の休止を設け、休止後、同じ温度環境下にて、直前に行われた放電と同じ電気量を90mA電流値で充電し、さらに1時間の休止を設けた。この操作により、放電前の状態が常にSOC100%となるように調整した。次に、電池を25℃の温度環境下に戻し、5時間以上放置した後、同様の手順により、900mA、1350mA、1800mA及び2250mAの各電流値で各30秒の放電を行った。
V = E0 + IR (R<0)
W = I × V = (1.5−E0)/R × 1.5
以下に示す種々の組成の電解液を調整し、非水電解質として用いた。ここで、EMCはエチルメチルカーボネート、VCはビニレンカーボネート、PCはプロピレンカーボネート、ECはエチレンカーボネート、DMCはジメチルカーボネート、DECはジエチルカーボネートを表す。
〔1〕1.2M LiPF6 EMC + 1質量% VC
〔2〕1.2M LiPF6 PC:EMC=2:98(体積%)+ 1質量% VC
〔3〕1.2M LiPF6 PC:EMC=4:96(体積%)+ 1質量% VC
〔4〕1.2M LiPF6 PC:EMC=6:94(体積%)+ 1質量% VC
〔5〕1.2M LiPF6 PC:EMC=8:92(体積%)+ 1質量% VC
〔6〕1.2M LiPF6 PC:EMC=10:90(体積%)+ 1質量% VC
〔7〕1.2M LiPF6 PC:EMC=30:70(体積%)+ 1質量% VC
〔8〕1.2M LiPF6 PC:EMC=50:50(体積%)+ 1質量% VC
〔9〕1.2M LiPF6 EC:EMC=10:90(体積%)+ 1質量% VC
〔10〕1.2M LiPF6 DMC: EMC=10:90(体積%)+ 1質量% VC
〔11〕1.2M LiPF6 DEC: EMC=10:90(体積%)+ 1質量% VC
〔12〕1.2M LiPF6 DMC: EMC=20:80(体積%)+ 1質量% VC
〔13〕1.2M LiPF6 DMC: EMC=40:60(体積%)+ 1質量% VC
〔14〕1.2M LiPF6 DMC: EMC=50:50(体積%)+ 1質量% VC
〔15〕1.2M LiPF6 DMC: EMC=60:40(体積%)+ 1質量% VC
上記〔1〕〜〔6〕の非水電解質を用いた電池について、非水溶媒が含有する炭素−炭素二重結合を有さない炭酸エステルの体積に占める環状炭酸エステルの体積割合aの値を種々変化させた場合の試験結果を整理して表1に示す。
表1の結果において、非水電解質が環状炭酸エステルを含有しなくても、電池性能に遜色がないばかりか、低温出力性能に優れるものとなったという上記驚くべき現象を理解するために、電池の製造工程中に行われる初期充放電工程の条件を故意に過充電条件としたことを除いては同様の処方とし、上記実験No.1-1〜1-6の挙動と比較した。
上記〔1〕及び〔6〕〜〔8〕の非水電解質を用いた電池について、次の手順で60℃放置試験を行った。即ち、完成後の電池について、上記(電池容量試験及び電池厚み測定)の欄に記載した通りの手順で電池容量試験及び電池厚み測定を行った後、温度60℃の高温環境下で60日間、無負荷状態にて放置した。高温放置中、30日毎に電池を取り出し、上記(出力特性試験)の欄に記載した通りの条件で出力特性試験を行った。結果を表3に示す。
上記〔1〕、〔6〕、〔9〕〜〔11〕の非水電解質を用いた電池について、エチルメチルカーボネートと混合するエチルメチルカーボネート以外の炭酸エステルの種類を種々変更した場合の試験結果を整理して表4に示す。
上記〔1〕,〔10〕,〔12〕〜〔15〕の非水電解質を用いた電池について、エチルメチルカーボネートと混合するジメチルカーボネートの量を種々変更した場合の試験結果を整理して表5に示す。
上記[実験5]で用いた電池について、上記[実験3]の欄に記載したと同様の手順により、60℃放置試験を行った。結果を表6に示す。
Claims (3)
- 電解質塩と非水溶媒を含む非水電解質、正極、及びリチウム電位に対して1.2V以上の電位にてリチウムイオンが挿入・脱離する負極活物質を有する負極を備えた非水電解質電池において、前記非水溶媒が含有する炭素−炭素二重結合を有さない炭酸エステルの体積を100とし、該炭酸エステルのうち環状炭酸エステルの体積をa、ジメチルカーボネートの体積をb、エチルメチルカーボネートの体積をc、ジエチルカーボネートの体積をdとしたとき、a=0、10≦b<60、0<c≦90及び0≦d<10を同時に満たすことを特徴とする非水電解質電池。
- 前記負極活物質が、スピネル型チタン酸リチウムであることを特徴とする請求項1に記載の非水電解質電池。
- 満充電状態での正極電位が金属リチウムの電位に対して4.3V以下である請求項1又は2記載の非水電解質電池。
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