JP5441221B2 - 非水電解質二次電池及び非水電解質二次電池用非水電解液 - Google Patents
非水電解質二次電池及び非水電解質二次電池用非水電解液 Download PDFInfo
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 69
- 239000007773 negative electrode material Substances 0.000 claims description 53
- -1 alkylene diisocyanate compound Chemical class 0.000 claims description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 22
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 19
- 239000003125 aqueous solvent Substances 0.000 claims description 18
- 229910000676 Si alloy Inorganic materials 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- LLFXBHBGYSUGGF-UHFFFAOYSA-N [Li].FP(F)(F)=O Chemical compound [Li].FP(F)(F)=O LLFXBHBGYSUGGF-UHFFFAOYSA-N 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 8
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 19
- 239000008151 electrolyte solution Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 2
- LMUISDJVRQDLEK-UHFFFAOYSA-N 6,7-dichloro-1-[(3,4-dimethoxyphenyl)methyl]isoquinoline Chemical compound C1=C(OC)C(OC)=CC=C1CC1=NC=CC2=CC(Cl)=C(Cl)C=C12 LMUISDJVRQDLEK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IYJMQRLCWBFHJL-UHFFFAOYSA-N 1,11-diisocyanatoundecane Chemical compound O=C=NCCCCCCCCCCCN=C=O IYJMQRLCWBFHJL-UHFFFAOYSA-N 0.000 description 1
- UTFSEWQOIIZLRH-UHFFFAOYSA-N 1,7-diisocyanatoheptane Chemical compound O=C=NCCCCCCCN=C=O UTFSEWQOIIZLRH-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- GHSZVIPKVOEXNX-UHFFFAOYSA-N 1,9-diisocyanatononane Chemical compound O=C=NCCCCCCCCCN=C=O GHSZVIPKVOEXNX-UHFFFAOYSA-N 0.000 description 1
- ZTTYKFSKZIRTDP-UHFFFAOYSA-N 4,4-difluoro-1,3-dioxolan-2-one Chemical compound FC1(F)COC(=O)O1 ZTTYKFSKZIRTDP-UHFFFAOYSA-N 0.000 description 1
- PYKQXOJJRYRIHH-UHFFFAOYSA-N 4-fluoro-4-methyl-1,3-dioxolan-2-one Chemical compound CC1(F)COC(=O)O1 PYKQXOJJRYRIHH-UHFFFAOYSA-N 0.000 description 1
- LECKFEZRJJNBNI-UHFFFAOYSA-N 4-fluoro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1F LECKFEZRJJNBNI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017873 Cu—Ni—Si—Mg Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 229910021439 lithium cobalt complex oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M10/0568—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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- Secondary Cells (AREA)
Description
〔正極の作製〕
正極活物質としては、LiCoO2で表されるコバルト酸リチウム(平均粒子径13μm、BET比表面積0.35m2/g)の表面にジルコニウム化合物を固着させたものを用いた。表面にジルコニウム化合物が付着したコバルト酸リチウムは、原料中にジルコニウム化合物を添加し焼成することにより製造することができる。
負極活物質としては、平均粒子径が10μmのシリコン粉末(純度99.9質量%)を用いた。
非水系溶媒として、4−フルオロ−1,3−ジオキラン−2−オン(フルオロエチレンカーボネート:FEC)と、ジメチルカーボネート(DMC)とを用いた。添加剤として、1,6−ジイソシアナトヘキサン(HMDI)とを用いた。FEC:DMC:HMDIが20:79:1の体積比となるように混合し、混合溶媒を作製した。この混合溶媒に、溶質としてLiPF6を1.0モル/リットルの濃度となるように溶解させ、さらにジフルオロ燐酸リチウム(LiPF2O2)を1.0質量%となるように溶解させた。これに炭酸ガスを0.4質量%溶解させて、非水電解液を作製した。
上記で作製した正極、負極、及び非水電解液を用いて非水電解質二次電池を作製した。正極と負極とはセパレータを介して対向するように配置し、これらを所定の位置で折り曲げるようにして巻回し、これをプレスして扁平形状の電極体を作製した。
ジイソシアネート化合物として、HMDIに代えて、1,12−ジイソシアナトドデカン(DMDI)を用いる以外は、上記実施例1と同様にして非水電解質二次電池を作製した。
LiPF2O2の非水電解液中での含有量を0.5質量%とする以外は、実施例1と同様にして非水電解質二次電池を作製した。
FEC:DMC:HMDIを20:79.5:0.5の体積比とし、LiPF2O2を0.5質量%とする以外は、実施例1と同様にして非水電解質二次電池を作製した。
LiPF2O2及びHMDIを添加せずに、DMCの含有量を80体積%とする以外は、実施例1と同様にして非水電解質二次電池を作製した。
添加剤としてLiPF2O2のみを1質量%添加した以外は、実施例1と同様にして非水電解質二次電池を作製した。
添加剤としてHMDIのみを1体積%添加し、DMCの含有量を79体積%とする以外は、実施例1と同様にして非水電解質二次電池を作製した。
添加剤として、HMDIに代えてイソシアン酸ヘキシルを用いること以外は、実施例1と同様にして非水電解質二次電池を作製した。
DMCに代えて、プロピオン酸メチル(MP)を79体積%となるように用いる以外は、実施例1と同様にして非水電解質二次電池を作製した。
LiPF2O2及びHMDIを添加せず、DMCに代えてMPを80体積%用いる以外は、実施例1と同様にして非水電解質二次電池を作製した。
実施例1〜4及び比較例1〜6の各非水電解質二次電池について、それぞれ25℃の室温条件において、190mAの定電流で4.2Vになるまで充電し、さらに4.2Vの定電圧で電流値が48mAになるまで定電圧充電させた後、190mAの定電流で2.75Vになるまで放電させて、初期充放電を行った。
実施例1〜4及び比較例1〜6の各電池の電解液組成と共に、容量維持率を表1に示す。
1a…正極集電タブ
2…負極
2a…負極集電タブ
3…セパレータ
10…電極体
20…電池容器
Claims (4)
- 正極活物質を含む正極と、負極活物質を含む負極と、非水系溶媒に溶質を溶解させた非水電解液とを備える非水電解質二次電池であって、
前記負極活物質として、粉末状のシリコン及び/またはシリコン合金が用いられ、前記非水電解液に、モノフルオロ燐酸リチウム、ジフルオロ燐酸リチウム、トリフルオロ燐酸リチウムからなる群より選ばれる少なくとも1種のフッ素化燐酸リチウム、及び脂肪族炭化水素基の炭素数が6以上12以下であるアルキレンジイソシアネート化合物が添加剤として含まれ、鎖状カーボネート化合物が前記非水系溶媒として含まれていることを特徴とする非水電解質二次電池。 - 前記鎖状カーボネート化合物が、ジメチルカーボネートであることを特徴とする請求項1に記載の非水電解質二次電池。
- 前記非水系溶媒として、フッ素化環状カーボネートがさらに含有されていることを特徴とする請求項1または2に記載の非水電解質二次電池。
- 非水系溶媒と、非水系溶媒に溶解させた溶質とを含み、粉末状のシリコン及び/またはシリコン合金を負極活物質として用いる非水電解質二次電池に用いられる非水電解液であって、
モノフルオロ燐酸リチウム、ジフルオロ燐酸リチウム、トリフルオロ燐酸リチウムからなる群より選ばれる少なくとも1種のフッ素化燐酸リチウム、及び脂肪族炭化水素基の炭素数が6以上12以下であるアルキレンジイソシアネート化合物を添加剤として含み、鎖状カーボネート化合物を前記非水系溶媒として含むことを特徴とする非水電解質二次電池用非水電解液。
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CN105074994B (zh) * | 2013-03-27 | 2018-10-19 | 三菱化学株式会社 | 非水电解液及使用该非水电解液的非水电解质电池 |
WO2014197675A2 (en) | 2013-06-05 | 2014-12-11 | The Regents Of The University Of California | Mitigating thermal runaway in lithium ion batteries using damage-initiating materials or devices |
US10115942B2 (en) * | 2013-06-05 | 2018-10-30 | The Regents Of The University Of California | Rate-sensitive and self-releasing battery cells and battery-cell structures as structural and/or energy-absorbing vehicle components |
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