JP2021190184A - Non-aqueous electrolyte power storage element - Google Patents
Non-aqueous electrolyte power storage element Download PDFInfo
- Publication number
- JP2021190184A JP2021190184A JP2020091276A JP2020091276A JP2021190184A JP 2021190184 A JP2021190184 A JP 2021190184A JP 2020091276 A JP2020091276 A JP 2020091276A JP 2020091276 A JP2020091276 A JP 2020091276A JP 2021190184 A JP2021190184 A JP 2021190184A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- aqueous electrolyte
- electrode active
- negative electrode
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 99
- 238000003860 storage Methods 0.000 title claims abstract description 72
- 239000010954 inorganic particle Substances 0.000 claims abstract description 63
- 239000007774 positive electrode material Substances 0.000 claims abstract description 43
- 239000007773 negative electrode material Substances 0.000 claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 33
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 32
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 26
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 22
- 230000001629 suppression Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 115
- 239000000463 material Substances 0.000 description 36
- -1 lithium transition metal Chemical class 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 150000005678 chain carbonates Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 210000001787 dendrite Anatomy 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 238000007600 charging Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 239000002905 metal composite material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical class O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical class CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- IOBWAHRFIPQEQL-UHFFFAOYSA-N 1,3-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C=CC=C1F IOBWAHRFIPQEQL-UHFFFAOYSA-N 0.000 description 1
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical class O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 1
- HUDMAQLYMUKZOZ-UHFFFAOYSA-N 1,4-difluoro-2-methoxybenzene Chemical compound COC1=CC(F)=CC=C1F HUDMAQLYMUKZOZ-UHFFFAOYSA-N 0.000 description 1
- GUYHXQLLIISBQF-UHFFFAOYSA-N 1-cyclohexyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C1CCCCC1 GUYHXQLLIISBQF-UHFFFAOYSA-N 0.000 description 1
- YAOIFBJJGFYYFI-UHFFFAOYSA-N 1-cyclohexyl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1C1CCCCC1 YAOIFBJJGFYYFI-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- 125000004778 2,2-difluoroethyl group Chemical group [H]C([H])(*)C([H])(F)F 0.000 description 1
- CRMJLJFDPNJIQA-UHFFFAOYSA-N 2,4-difluoro-1-methoxybenzene Chemical compound COC1=CC=C(F)C=C1F CRMJLJFDPNJIQA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 description 1
- HHCHLHOEAKKCAB-UHFFFAOYSA-N 2-oxaspiro[3.5]nonane-1,3-dione Chemical compound O=C1OC(=O)C11CCCCC1 HHCHLHOEAKKCAB-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 description 1
- SROHGOJDCAODGI-UHFFFAOYSA-N 4,5-diphenyl-1,3-dioxol-2-one Chemical compound O1C(=O)OC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 SROHGOJDCAODGI-UHFFFAOYSA-N 0.000 description 1
- BQNCWEZBSRCWHT-UHFFFAOYSA-N 4-(2,2,2-trifluoroethyl)-1,3-dioxolan-2-one Chemical compound FC(F)(F)CC1COC(=O)O1 BQNCWEZBSRCWHT-UHFFFAOYSA-N 0.000 description 1
- RNNVXAXTORCUFA-UHFFFAOYSA-N 4-(fluoromethyl)-1,3-dioxolan-2-one Chemical compound FCC1COC(=O)O1 RNNVXAXTORCUFA-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- VMAJRFCXVOIAAS-UHFFFAOYSA-N 4-phenyl-1,3-dioxol-2-one Chemical compound O1C(=O)OC=C1C1=CC=CC=C1 VMAJRFCXVOIAAS-UHFFFAOYSA-N 0.000 description 1
- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 229910012424 LiSO 3 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- PMGBATZKLCISOD-UHFFFAOYSA-N methyl 3,3,3-trifluoropropanoate Chemical compound COC(=O)CC(F)(F)F PMGBATZKLCISOD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- ZDCRNXMZSKCKRF-UHFFFAOYSA-N tert-butyl 4-(4-bromoanilino)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1NC1=CC=C(Br)C=C1 ZDCRNXMZSKCKRF-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
Description
本発明は、非水電解質蓄電素子に関する。 The present invention relates to a non-aqueous electrolyte power storage device.
リチウムイオン二次電池に代表される非水電解質二次電池は、エネルギー密度の高さから、パーソナルコンピュータ、通信端末等の電子機器、自動車等に多用されている。上記非水電解質二次電池は、一般的には、セパレータで電気的に隔離された一対の電極と、この電極間に介在する非水電解質とを有し、両電極間でイオンの受け渡しを行うことで充放電するよう構成される。また、非水電解質二次電池以外の非水電解質蓄電素子として、リチウムイオンキャパシタや電気二重層キャパシタ等のキャパシタも広く普及している。 Non-aqueous electrolyte secondary batteries typified by lithium ion secondary batteries are widely used in personal computers, electronic devices such as communication terminals, automobiles, etc. due to their high energy density. The non-aqueous electrolyte secondary battery generally has a pair of electrodes electrically separated by a separator and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the two electrodes. It is configured to charge and discharge. In addition, capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as non-aqueous electrolyte storage elements other than non-aqueous electrolyte secondary batteries.
近年、非水電解質二次電池の高容量化に向けて、負極の高容量化が求められている。リチウム金属は、現在リチウムイオン二次電池の負極活物質として広く用いられている黒鉛と比較すると活物質質量あたりの放電容量が著しく大きい。このため、負極活物質としてリチウム金属を用いた非水電解質二次電池が提案されている（特開２０１１−１２４１５４号公報参照）。 In recent years, in order to increase the capacity of non-aqueous electrolyte secondary batteries, it has been required to increase the capacity of the negative electrode. Lithium metal has a significantly larger discharge capacity per active material mass than graphite, which is currently widely used as a negative electrode active material for lithium ion secondary batteries. Therefore, a non-aqueous electrolyte secondary battery using a lithium metal as a negative electrode active material has been proposed (see JP-A-2011-124154).
しかしながら、負極活物質にリチウム金属が用いられた非水電解質蓄電素子においては、充電の際に負極表面でリチウム金属が樹枝状に析出することがある（以下、樹枝状の形態をしたリチウム金属を「デンドライト」という。）。このデンドライトが成長すると、セパレータを貫通して正極と接触し、短絡を引き起こすおそれがある。 However, in a non-aqueous electrolyte power storage element in which lithium metal is used as the negative electrode active material, lithium metal may precipitate in a dendritic shape on the surface of the negative electrode during charging (hereinafter, lithium metal in a dendritic form). It is called "Dendrite"). When this dendrite grows, it may penetrate the separator and come into contact with the positive electrode, causing a short circuit.
本発明は、以上のような事情に基づいてなされたものであり、短絡発生に対する抑制効果が高い非水電解質蓄電素子を提供することを目的とする。 The present invention has been made based on the above circumstances, and an object of the present invention is to provide a non-aqueous electrolyte power storage element having a high effect of suppressing the occurrence of a short circuit.
上記課題を解決するためになされた本発明の一側面は、負極活物質層を有する負極と、正極活物質層を有する正極と、非水溶媒を含有する非水電解質と、上記負極活物質層及び上記正極活物質層間に介在するセパレータと、上記セパレータ及び上記負極活物質層間に介在する第１無機粒子層とを備え、上記負極活物質層がリチウム金属を含み、上記非水溶媒がフッ素化カーボネートを含む非水電解質蓄電素子である。 One aspect of the present invention made to solve the above problems is a negative electrode having a negative electrode active material layer, a positive electrode having a positive electrode active material layer, a non-aqueous electrolyte containing a non-aqueous solvent, and the negative electrode active material layer. A separator interposed between the positive electrode active material layers and a first inorganic particle layer interposed between the separator and the negative electrode active material layers are provided, the negative electrode active material layer contains a lithium metal, and the non-aqueous solvent is fluorinated. It is a non-aqueous electrolyte storage element containing a carbonate.
本発明によれば、短絡発生に対する抑制効果が高い非水電解質蓄電素子を提供することができる。 According to the present invention, it is possible to provide a non-aqueous electrolyte power storage element having a high effect of suppressing the occurrence of a short circuit.
初めに、本明細書によって開示される非水電解質蓄電素子の概要について説明する。 First, the outline of the non-aqueous electrolyte power storage device disclosed by the present specification will be described.
本発明の一側面に係る非水電解質蓄電素子は、負極活物質層を有する負極と、正極活物質層を有する正極と、非水溶媒を含有する非水電解質と、上記負極活物質層及び上記正極活物質層間に介在するセパレータと、上記セパレータ及び上記負極活物質層間に介在する第１無機粒子層とを備え、上記負極活物質層がリチウム金属を含み、上記非水溶媒がフッ素化カーボネートを含む。 The non-aqueous electrolyte power storage element according to one aspect of the present invention includes a negative electrode having a negative electrode active material layer, a positive electrode having a positive electrode active material layer, a non-aqueous electrolyte containing a non-aqueous solvent, the negative electrode active material layer, and the above. A separator interposed between the positive electrode active material layers and a first inorganic particle layer interposed between the separator and the negative electrode active material layers are provided, the negative electrode active material layer contains a lithium metal, and the non-aqueous solvent contains a fluorinated carbonate. include.
当該非水電解質蓄電素子によれば、短絡発生に対する抑制効果が高い。この理由は定かではないが、以下の理由が推測される。当該非水電解質蓄電素子の非水電解質が、非水溶媒としてフッ素化カーボネートを含むことで、負極活物質層表面において、フッ素化カーボネートの還元分解生成物であるフッ化リチウムの含有率が高い被膜が形成される。このフッ化リチウムの含有率が高い被膜は均一かつ安定であり、電流分布が均一に維持されるので、デンドライトの形成が抑制される。また、負極活物質層がリチウム金属を含み、上記負極活物質層及び上記セパレータ間に第１無機粒子層が介在することで、リチウム金属の体積変化に起因する圧迫によるセパレータの細孔の閉塞に対する耐性が高まる。このため、リチウム金属とセパレータとの界面における電流分布が均一に維持されるので、デンドライトの形成が抑制される。このように、当該非水電解質蓄電素子はデンドライトの形成に対する抑制効果に優れる結果、短絡発生に対する抑制効果が高い。 According to the non-aqueous electrolyte power storage element, the effect of suppressing the occurrence of a short circuit is high. The reason for this is not clear, but the following reasons are presumed. Since the non-aqueous electrolyte of the non-aqueous electrolyte power storage element contains fluorinated carbonate as a non-aqueous solvent, a film having a high content of lithium fluoride, which is a reduction decomposition product of fluorinated carbonate, on the surface of the negative electrode active material layer. Is formed. This coating film having a high lithium fluoride content is uniform and stable, and the current distribution is maintained uniformly, so that the formation of dendrites is suppressed. Further, the negative electrode active material layer contains lithium metal, and the first inorganic particle layer is interposed between the negative electrode active material layer and the separator, so that the pores of the separator are blocked due to compression due to the volume change of the lithium metal. Increased resistance. Therefore, the current distribution at the interface between the lithium metal and the separator is maintained uniformly, and the formation of dendrites is suppressed. As described above, the non-aqueous electrolyte power storage element is excellent in suppressing the formation of dendrites, and as a result, is highly effective in suppressing the occurrence of short circuits.
上記フッ素化カーボネートがフッ素化環状カーボネートを含むことが好ましい。上記フッ素化カーボネートがフッ素化環状カーボネートを含むことで、当該非水電解質蓄電素子のデンドライトの形成に対する抑制効果をより高めることができる。 It is preferable that the fluorinated carbonate contains a fluorinated cyclic carbonate. When the fluorinated carbonate contains a fluorinated cyclic carbonate, the effect of suppressing the formation of dendrites of the non-aqueous electrolyte power storage device can be further enhanced.
上記非水溶媒における上記フッ素化環状カーボネートの含有量が１０体積％以上５０体積％以下であることが好ましい。上記非水溶媒における上記フッ素化環状カーボネートの含有量が上記範囲であることで、当該非水電解質蓄電素子のデンドライトの形成に対する抑制効果をより高めることができる。 The content of the fluorinated cyclic carbonate in the non-aqueous solvent is preferably 10% by volume or more and 50% by volume or less. When the content of the fluorinated cyclic carbonate in the non-aqueous solvent is in the above range, the effect of suppressing the formation of dendrites of the non-aqueous electrolyte power storage device can be further enhanced.
上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することが好ましい。上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することで、長期の充放電サイクル時の正極活物質層表面における非水電解質の分解生成物によるセパレータの目詰まりなどが、多孔質の第２無機粒子層によって抑制される。その結果、正極とセパレータとの界面における電流分布が均一に維持されると考えられる。従って、上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することで、短絡の発生に対する抑制効果をより向上できる。 It is preferable to further have a second inorganic particle layer interposed between the separator and the positive electrode active material layer. By further having the second inorganic particle layer interposed between the separator and the positive electrode active material layer, clogging of the separator due to the decomposition product of the non-aqueous electrolyte on the surface of the positive electrode active material layer during a long-term charge / discharge cycle can be prevented. It is suppressed by the porous second inorganic particle layer. As a result, it is considered that the current distribution at the interface between the positive electrode and the separator is maintained uniformly. Therefore, by further having the second inorganic particle layer interposed between the separator and the positive electrode active material layer, the effect of suppressing the occurrence of a short circuit can be further improved.
以下、本発明の一実施形態に係る非水電解質蓄電素子について詳説する。なお、各実施形態に用いられる各構成部材（各構成要素）の名称は、背景技術に用いられる各構成部材（各構成要素）の名称と異なる場合がある。 Hereinafter, the non-aqueous electrolyte power storage device according to the embodiment of the present invention will be described in detail. The name of each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background technology.
＜非水電解質蓄電素子＞
本発明の一実施形態に係る非水電解質蓄電素子は、負極と、正極と、非水電解質とを備える。以下、非水電解質蓄電素子の一例として、非水電解質二次電池について説明する。上記正極及び負極は、通常、セパレータを介して積層又は巻回により交互に重畳された電極体を形成する。この電極体はケースに収納され、このケース内に非水電解質が充填される。上記非水電解質は、正極と負極との間に介在する。また、上記ケースとしては、非水電解質二次電池のケースとして通常用いられる公知の金属ケース、樹脂ケース等を用いることができる。
<Non-water electrolyte power storage element>
The non-aqueous electrolyte power storage element according to the embodiment of the present invention includes a negative electrode, a positive electrode, and a non-aqueous electrolyte. Hereinafter, the non-aqueous electrolyte secondary battery will be described as an example of the non-aqueous electrolyte power storage element. The positive electrode and the negative electrode usually form an electrode body that is alternately superposed by laminating or winding through a separator. The electrode body is housed in a case, and the case is filled with a non-aqueous electrolyte. The non-aqueous electrolyte is interposed between the positive electrode and the negative electrode. Further, as the above case, a known metal case, resin case or the like which is usually used as a case of a non-aqueous electrolyte secondary battery can be used.
［負極］
負極は、負極基材と、上記負極基材の少なくとも一方の面に直接又は間接に積層される負極活物質層とを備える。負極は、負極基材と負極活物質層との間に配される中間層を備えていてもよい。
[Negative electrode]
The negative electrode includes a negative electrode base material and a negative electrode active material layer directly or indirectly laminated on at least one surface of the negative electrode base material. The negative electrode may include an intermediate layer arranged between the negative electrode base material and the negative electrode active material layer.
（負極基材）
負極基材は、導電性を有する。負極基材の材質としては、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の金属又はこれらの合金が用いられる。これらの中でも銅又は銅合金が好ましい。負極基材としては、箔、蒸着膜等が挙げられ、コストの観点から箔が好ましい。したがって、負極基材としては銅箔又は銅合金箔が好ましい。銅箔の例としては、圧延銅箔、電解銅箔等が挙げられる。なお、「導電性」を有するとは、ＪＩＳ−Ｈ０５０５（１９７５）に準拠して測定される体積抵抗率が１×１０７Ω・ｃｍ以下であることを意味し、「非導電性」とは、上記体積抵抗率が１×１０７Ω・ｃｍ超であることを意味する。
(Negative electrode base material)
The negative electrode substrate has conductivity. As the material of the negative electrode base material, a metal such as copper, nickel, stainless steel, nickel-plated steel or an alloy thereof is used. Among these, copper or a copper alloy is preferable. Examples of the negative electrode base material include a foil and a vapor-deposited film, and the foil is preferable from the viewpoint of cost. Therefore, a copper foil or a copper alloy foil is preferable as the negative electrode base material. Examples of the copper foil include rolled copper foil, electrolytic copper foil and the like. Incidentally, to have a "conductive" means that the volume resistivity is measured according to JIS-H0505 (1975) is not more than 1 × 10 7 Ω · cm, and "non-conductive" are means that the volume resistivity is 1 × 10 7 Ω · cm greater.
負極基材の平均厚さは、２μｍ以上３５μｍ以下が好ましく、３μｍ以上３０μｍ以下がより好ましく、４μｍ以上２５μｍ以下がさらに好ましく、５μｍ以上２０μｍ以下が特に好ましい。負極基材の平均厚さを上記の範囲とすることで、負極基材の強度を高めつつ、非水電解質二次電池の体積当たりのエネルギー密度を高めることができる。「基材の平均厚さ」とは、所定の面積の基材を打ち抜いた際の打ち抜き質量を、基材の真密度及び打ち抜き面積で除した値をいう。 The average thickness of the negative electrode substrate is preferably 2 μm or more and 35 μm or less, more preferably 3 μm or more and 30 μm or less, further preferably 4 μm or more and 25 μm or less, and particularly preferably 5 μm or more and 20 μm or less. By setting the average thickness of the negative electrode base material within the above range, it is possible to increase the energy density per volume of the non-aqueous electrolyte secondary battery while increasing the strength of the negative electrode base material. The "average thickness of the base material" means a value obtained by dividing the punching mass when punching a base material having a predetermined area by the true density of the base material and the punched area.
（負極活物質層）
上記負極活物質層は、負極活物質としてリチウム金属を含む。負極活物質がリチウム金属を含むことで活物質質量あたりの放電容量を向上できる。上記リチウム金属には、リチウム単体の他、リチウム合金が含まれる。リチウム合金としては、例えば、リチウムアルミニウム合金、リチウムマグネシウム合金、リチウムインジウム合金等が挙げられる。リチウム金属を含む負極活物質層は、箔状のリチウム金属を所定の形状に切断するか、圧延、蒸着等により所定の形状に成形することにより製造できる。
(Negative electrode active material layer)
The negative electrode active material layer contains lithium metal as the negative electrode active material. Since the negative electrode active material contains lithium metal, the discharge capacity per active material mass can be improved. The lithium metal includes a lithium alloy as well as a simple substance of lithium. Examples of the lithium alloy include a lithium aluminum alloy, a lithium magnesium alloy, a lithium indium alloy and the like. The negative electrode active material layer containing a lithium metal can be manufactured by cutting a foil-shaped lithium metal into a predetermined shape, or forming the foil-shaped lithium metal into a predetermined shape by rolling, vapor deposition, or the like.
さらに、負極活物質層は、Ｎａ、Ｋ、Ｃａ、Ｆｅ、Ｍｇ、Ｓｉ、Ｎ等の元素を含有してもよい。 Further, the negative electrode active material layer may contain elements such as Na, K, Ca, Fe, Mg, Si and N.
上記負極活物質に占めるリチウム金属の含有量の下限としては、８０質量％が好ましく、９０質量％がより好ましく、９５質量％がさらに好ましい。一方、この含有量の上限は、１００質量％であってよい。 The lower limit of the content of the lithium metal in the negative electrode active material is preferably 80% by mass, more preferably 90% by mass, and even more preferably 95% by mass. On the other hand, the upper limit of this content may be 100% by mass.
［正極］
正極は、正極基材と、正極活物質層とを有する。上記正極活物質層は、正極活物質を含有する。上記正極活物質層は、上記正極基材の少なくとも一方の面に沿って直接又は中間層を介して積層される。
[Positive electrode]
The positive electrode has a positive electrode base material and a positive electrode active material layer. The positive electrode active material layer contains a positive electrode active material. The positive electrode active material layer is laminated directly or via an intermediate layer along at least one surface of the positive electrode base material.
上記正極基材は、導電性を有する。基材の材質としては、アルミニウム、チタン、タンタル、ステンレス鋼等の金属又はそれらの合金が用いられる。これらの中でも、耐電位性、導電性の高さ及びコストのバランスからアルミニウム及びアルミニウム合金が好ましい。また、正極基材の形態としては、箔、蒸着膜等が挙げられ、コストの面から箔が好ましい。つまり、正極基材としてはアルミニウム箔が好ましい。なお、アルミニウム又はアルミニウム合金としては、ＪＩＳ−Ｈ４０００（２０１４）に規定されるＡ１０８５、Ａ３００３等が例示できる。 The positive electrode base material has conductivity. As the material of the base material, metals such as aluminum, titanium, tantalum, and stainless steel or alloys thereof are used. Among these, aluminum and aluminum alloys are preferable from the viewpoint of the balance between potential resistance, high conductivity and cost. Further, examples of the form of the positive electrode base material include a foil and a vapor-deposited film, and the foil is preferable from the viewpoint of cost. That is, aluminum foil is preferable as the positive electrode base material. Examples of aluminum or aluminum alloy include A1085 and A3003 specified in JIS-H4000 (2014).
正極活物質層は、正極活物質を含むいわゆる正極合剤から形成される。また、正極活物質層は、必要に応じて導電剤、バインダー、増粘剤、フィラー等の任意成分を含む。 The positive electrode active material layer is formed from a so-called positive electrode mixture containing a positive electrode active material. Further, the positive electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, and a filler, if necessary.
上記正極活物質としては、例えば、公知の正極活物質の中から適宜選択できる。リチウムイオン二次電池用の正極活物質としては、通常、リチウムイオンを吸蔵及び放出することができる材料が用いられる。正極活物質としては、例えば、α−ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物、スピネル型結晶構造を有するリチウム遷移金属複合酸化物、ポリアニオン化合物、カルコゲン化合物、硫黄等が挙げられる。α−ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物として、例えば、Ｌｉ［ＬｉｘＮｉ１−ｘ］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＣｏ（１−ｘ−γ）］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＣｏ（１−ｘ）］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＭｎ（１−ｘ−γ）］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＮｉγＭｎβＣｏ（１−ｘ−γ−β）］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β≦１）、Ｌｉ［ＬｉｘＮｉγＣｏβＡｌ（１−ｘ−γ−β）］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β＜１）等が挙げられる。スピネル型結晶構造を有するリチウム遷移金属複合酸化物として、ＬｉｘＭｎ２Ｏ４、ＬｉｘＮｉγＭｎ（２−γ）Ｏ４等が挙げられる。ポリアニオン化合物として、ＬｉＦｅＰＯ４、ＬｉＭｎＰＯ４、ＬｉＮｉＰＯ４、ＬｉＣｏＰＯ４、Ｌｉ３Ｖ２（ＰＯ４）３、Ｌｉ２ＭｎＳｉＯ４、Ｌｉ２ＣｏＰＯ４Ｆ等が挙げられる。カルコゲン化合物として、二硫化チタン、二硫化モリブデン、二酸化モリブデン等が挙げられる。これらの材料中の原子又はポリアニオンは、他の元素からなる原子又はアニオン種で一部が置換されていてもよい。これらの材料は表面が他の材料で被覆されていてもよい。正極活物質層においては、これら材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。正極活物質層においては、これら化合物の１種を単独で用いてもよく、２種以上を混合して用いてもよい。正極活物質層中の正極活物質の含有量は特に限定されないが、その下限としては、５０質量％が好ましく、８０質量％がより好ましく、９０質量％がさらに好ましい。一方、この含有量の上限としては、９９質量％が好ましく、９８質量％がより好ましい。 As the positive electrode active material, for example, a known positive electrode active material can be appropriately selected. As the positive electrode active material for a lithium ion secondary battery, a material capable of occluding and releasing lithium ions is usually used. Examples of the positive electrode active material include a lithium transition metal composite oxide having an α-NaFeO type 2 crystal structure, a lithium transition metal composite oxide having a spinel type crystal structure, a polyanionic compound, a chalcogen compound, sulfur and the like. Examples of the lithium transition metal composite oxide having an α-NaFeO type 2 crystal structure include Li [Li x Ni 1-x ] O 2 (0 ≦ x <0.5) and Li [Li x Ni γ Co (1-). x-γ) ] O 2 (0 ≦ x <0.5, 0 <γ <1), Li [Li x Co (1-x) ] O 2 (0 ≦ x <0.5), Li [Li x Ni γ Mn (1-x-γ) ] O 2 (0 ≦ x <0.5, 0 <γ <1), Li [Li x Ni γ Mn β Co (1-x-γ-β) ] O 2 (0≤x <0.5, 0 <γ, 0 <β, 0.5 <γ + β≤1), Li [Li x Ni γ Co β Al (1-x-γ-β) ] O 2 (0≤ Examples thereof include x <0.5, 0 <γ, 0 <β, 0.5 <γ + β <1). Examples of the lithium transition metal composite oxide having a spinel-type crystal structure include Li x Mn 2 O 4 and Li x Ni γ Mn (2-γ) O 4 . Examples of the polyanionic compound include LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , Li 2 CoPO 4 F and the like. Examples of the chalcogen compound include titanium disulfide, molybdenum disulfide, molybdenum dioxide and the like. The atoms or polyanions in these materials may be partially substituted with atoms or anion species consisting of other elements. The surface of these materials may be coated with other materials. In the positive electrode active material layer, one of these materials may be used alone, or two or more of them may be mixed and used. In the positive electrode active material layer, one of these compounds may be used alone, or two or more thereof may be mixed and used. The content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but the lower limit thereof is preferably 50% by mass, more preferably 80% by mass, still more preferably 90% by mass. On the other hand, as the upper limit of this content, 99% by mass is preferable, and 98% by mass is more preferable.
導電剤は、導電性を有する材料であれば特に限定されない。このような導電剤としては、例えば、炭素質材料、金属、導電性セラミックス等が挙げられる。炭素質材料としては、黒鉛化炭素、非黒鉛化炭素、グラフェン系炭素等が挙げられる。非黒鉛化炭素としては、カーボンナノファイバー、ピッチ系炭素繊維、カーボンブラック等が挙げられる。カーボンブラックとしては、ファーネスブラック、アセチレンブラック、ケッチェンブラック等が挙げられる。グラフェン系炭素としては、グラフェン、カーボンナノチューブ（ＣＮＴ）、フラーレン等が挙げられる。導電剤の形状としては、粉状、繊維状等が挙げられる。導電剤としては、これらの材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。また、これらの材料を複合化して用いてもよい。例えば、カーボンブラックとＣＮＴとを複合化した材料を用いてもよい。これらの中でも、電子伝導性及び塗工性の観点よりカーボンブラックが好ましく、中でもアセチレンブラックが好ましい。 The conductive agent is not particularly limited as long as it is a conductive material. Examples of such a conductive agent include carbonaceous materials, metals, conductive ceramics and the like. Examples of the carbonaceous material include graphitized carbon, non-graphitized carbon, graphene-based carbon and the like. Examples of the non-graphitized carbon include carbon nanofibers, pitch-based carbon fibers, and carbon black. Examples of carbon black include furnace black, acetylene black, and ketjen black. Examples of graphene-based carbon include graphene, carbon nanotubes (CNT), fullerenes and the like. Examples of the shape of the conductive agent include powder and fibrous. As the conductive agent, one of these materials may be used alone, or two or more of them may be mixed and used. Further, these materials may be combined and used. For example, a material in which carbon black and CNT are combined may be used. Among these, carbon black is preferable from the viewpoint of electron conductivity and coatability, and acetylene black is particularly preferable.
正極活物質層における導電剤の含有量は、１質量％以上１０質量％以下が好ましく、３質量％以上９質量％以下がより好ましい。導電剤の含有量を上記の範囲とすることで、非水電解質二次電池のエネルギー密度を高めることができる。 The content of the conductive agent in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 9% by mass or less. By setting the content of the conductive agent in the above range, the energy density of the non-aqueous electrolyte secondary battery can be increased.
上記バインダーとしては、フッ素樹脂（ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等）、ポリエチレン、ポリプロピレン、ポリイミド等の熱可塑性樹脂；エチレンプロピレンジエンゴム（ＥＰＤＭ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のエラストマー；多糖類高分子等が挙げられる。正極活物質層におけるバインダーの含有量は、１質量％以上１０質量％以下が好ましく、３質量％以上９質量％以下がより好ましい。 Examples of the binder include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, and polyimide; ethylene propylene diene rubber (EPDM), sulfonated EPDM, and styrene butadiene. Elastomers such as rubber (SBR) and fluororubber; polysaccharide polymers and the like can be mentioned. The content of the binder in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 9% by mass or less.
上記増粘剤としては、例えばカルボキシメチルセルロース（ＣＭＣ）、メチルセルロース等の多糖類高分子が挙げられる。また、増粘剤がリチウムと反応する官能基を有する場合、予めメチル化等によりこの官能基を失活させておくことが好ましい。 Examples of the thickener include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose. When the thickener has a functional group that reacts with lithium, it is preferable to inactivate this functional group by methylation or the like in advance.
フィラーは、特に限定されない。フィラーとしては、ポリプロピレン、ポリエチレン等のポリオレフィン、二酸化ケイ素、アルミナ、二酸化チタン、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の無機酸化物、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物、炭酸カルシウム等の炭酸塩、フッ化カルシウム、フッ化バリウム、硫酸バリウム等の難溶性のイオン結晶、窒化アルミニウム、窒化ケイ素等の窒化物、タルク、モンモリロナイト、ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。 The filler is not particularly limited. Fillers include polyolefins such as polypropylene and polyethylene, silicon dioxide, alumina, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, inorganic oxides such as aluminosilicate, magnesium hydroxide, calcium hydroxide, and hydroxide. Hydroxides such as aluminum, carbonates such as calcium carbonate, sparingly soluble ion crystals such as calcium fluoride, barium fluoride, barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, zeolite, etc. Examples thereof include mineral resource-derived substances such as apatite, kaolin, mulite, spinel, olivine, sericite, bentonite, and mica, or man-made products thereof.
上記中間層は、正極基材の表面の被覆層であり、炭素粒子等の導電性粒子を含むことで正極基材と正極活物質層との接触抵抗を低減する。負極と同様、中間層の構成は特に限定されず、例えば樹脂バインダー及び導電性粒子を含有する組成物により形成できる。 The intermediate layer is a coating layer on the surface of the positive electrode base material, and contains conductive particles such as carbon particles to reduce the contact resistance between the positive electrode base material and the positive electrode active material layer. Similar to the negative electrode, the structure of the intermediate layer is not particularly limited, and can be formed by, for example, a composition containing a resin binder and conductive particles.
［非水電解質］
非水電解質は、非水溶媒及びこの非水溶媒に溶解している電解質塩を含有する。上記非水溶媒は、フッ素化カーボネートを含む。なお、上記非水電解質は、液体に限定されるものではない。すなわち、上記非水電解質は、液体状のものだけに限定されず、固体状やゲル状のもの等も含む。
[Non-water electrolyte]
The non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent. The non-aqueous solvent contains a fluorinated carbonate. The non-aqueous electrolyte is not limited to a liquid. That is, the non-aqueous electrolyte is not limited to a liquid state, but also includes a solid state, a gel state, and the like.
（非水溶媒）
上記非水溶媒は、フッ素化カーボネートを含む。上記非水溶媒は、フッ素化カーボネートを含むことで、負極活物質層表面において、フッ素化カーボネートの還元分解生成物であるフッ化リチウムの含有率が高い被膜が形成される。このフッ化リチウムの含有率が高い被膜は均一かつ安定であり、電流分布が均一に維持されるので、デンドライトの形成が抑制される。フッ素化カーボネートとは、カーボネートが有する水素原子の一部又は全部がフッ素原子で置換された化合物をいう。フッ素化カーボネートは、１種又は２種以上を用いることができる。上記フッ素化カーボネートとしては、フッ素化環状カーボネート及びフッ素化鎖状カーボネートが挙げられる。
(Non-aqueous solvent)
The non-aqueous solvent contains a fluorinated carbonate. By containing the fluorinated carbonate in the non-aqueous solvent, a film having a high content of lithium fluoride, which is a reduction decomposition product of the fluorinated carbonate, is formed on the surface of the negative electrode active material layer. This coating film having a high lithium fluoride content is uniform and stable, and the current distribution is maintained uniformly, so that the formation of dendrites is suppressed. The fluorinated carbonate refers to a compound in which a part or all of the hydrogen atom of the carbonate is replaced with a fluorine atom. As the fluorinated carbonate, one kind or two or more kinds can be used. Examples of the fluorinated carbonate include fluorinated cyclic carbonate and fluorinated chain carbonate.
上記フッ素化環状カーボネートとしては、例えばフルオロエチレンカーボネート（ＦＥＣ）、ジフルオロエチレンカーボネート等のフッ素化エチレンカーボネート、フルオロメチルエチレンカーボネート等のフッ素化プロピレンカーボネート、トリフルオロエチルエチレンカーボネート等のフッ素化ブチレンカーボネート等を挙げることができる。これらの中でも、フッ素化エチレンカーボネートが好ましく、フルオロエチレンカーボネートがより好ましい。上記フルオロエチレンカーボネートは耐酸化性が高く、非水電解質蓄電素子の充放電時に生じうる副反応（非水溶媒等の酸化分解等）の抑制効果が高い。また、フルオロエチレンカーボネートは比較的貴な電位で還元分解することで、リチウム金属上に速やかに安定な被膜を生成することから、リチウム金属上での継続的な非水電解質の還元分解を抑制することができる。 Examples of the fluorinated cyclic carbonate include fluorinated ethylene carbonate such as fluoroethylene carbonate (FEC) and difluoroethylene carbonate, fluorinated propylene carbonate such as fluoromethylethylene carbonate, and fluorinated butylene carbonate such as trifluoroethylethylene carbonate. Can be mentioned. Among these, fluorinated ethylene carbonate is preferable, and fluoroethylene carbonate is more preferable. The fluoroethylene carbonate has high oxidation resistance and is highly effective in suppressing side reactions (oxidative decomposition of non-aqueous solvents and the like) that may occur during charging and discharging of the non-aqueous electrolyte storage element. In addition, fluoroethylene carbonate rapidly forms a stable film on the lithium metal by reducing and decomposing it at a relatively noble potential, thus suppressing continuous reduction and decomposition of the non-aqueous electrolyte on the lithium metal. be able to.
フッ素化鎖状カーボネートとしては、例えばトリフルオロエチルメチルカーボネート（ＴＦＥＭＣ）、ビス（トリフルオロエチル）カーボネート（ＦＤＥＣ）等が挙げられる。 Examples of the fluorinated chain carbonate include trifluoroethyl methyl carbonate (TFEMC) and bis (trifluoroethyl) carbonate (FDEC).
上記フッ素化カーボネートがフッ素化環状カーボネートを含むことが好ましい。上記フッ素化カーボネートがフッ素化環状カーボネートを含むことで、当該非水電解質蓄電素子のデンドライトの形成に対する抑制効果をより高めることができる。また、フッ素化環状カーボネートとフッ素化鎖状カーボネートとを併用することがより好ましい。フッ素化鎖状カーボネートを用いることで、非水電解質の粘度を低く抑えることができる。フッ素化環状カーボネートとフッ素化鎖状カーボネートとを併用する場合、フッ素化環状カーボネートとフッ素化鎖状カーボネートとの体積比率（フッ素化環状カーボネート：フッ素化鎖状カーボネート）としては、例えば、５：９５から８０：２０の範囲が好ましく、２０：８０から７０：３０の範囲がより好ましく、３０：７０から６０：４０の範囲がさらに好ましく、４０：６０から５０：５０の範囲がよりさらに好ましいこともある。 It is preferable that the fluorinated carbonate contains a fluorinated cyclic carbonate. When the fluorinated carbonate contains a fluorinated cyclic carbonate, the effect of suppressing the formation of dendrites of the non-aqueous electrolyte power storage device can be further enhanced. Further, it is more preferable to use the fluorinated cyclic carbonate and the fluorinated chain carbonate in combination. By using the fluorinated chain carbonate, the viscosity of the non-aqueous electrolyte can be kept low. When the fluorinated cyclic carbonate and the fluorinated chain carbonate are used in combination, the volume ratio of the fluorinated cyclic carbonate and the fluorinated chain carbonate (fluorinated cyclic carbonate: fluorinated chain carbonate) is, for example, 5:95. The range from 80:20 is preferable, the range from 20:80 to 70:30 is more preferable, the range from 30:70 to 60:40 is even more preferable, and the range from 40:60 to 50:50 is even more preferable. be.
上記非水溶媒は、フッ素化カーボネート以外の有機溶媒を含有してもよい。他の有機溶媒としては、例えばフッ素化鎖状カーボネート以外の鎖状カーボネート、フッ素化環状カーボネート以外の環状カーボネート、エステル、エーテル、アミド、ラクトン、ニトリル、スルホン、サルファイト等を挙げることができる。 The non-aqueous solvent may contain an organic solvent other than the fluorinated carbonate. Examples of other organic solvents include chain carbonates other than fluorinated chain carbonates, cyclic carbonates other than fluorinated cyclic carbonates, esters, ethers, amides, lactones, nitriles, sulfones, sulfites and the like.
上記フッ素化鎖状カーボネート以外の鎖状カーボネートとしては、例えばジエチルカーボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭＣ）、ジメチルカーボネート（ＤＭＣ）、ジフェニルカーボネート等を挙げることができる。上記フッ素化環状カーボネート以外の環状カーボネートとしては、例えばエチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）、クロロエチレンカーボネート、スチレンカーボネート、カテコールカーボネート、１−フェニルビニレンカーボネート、１，２−ジフェニルビニレンカーボネート等を挙げることができる。 Examples of the chain carbonate other than the fluorinated chain carbonate include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diphenyl carbonate and the like. Examples of the cyclic carbonate other than the fluorinated cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), chloroethylene carbonate, and styrene carbonate. , Catecol carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate and the like.
上記エステルとしては、例えば３，３，３−トリフルオロプロピオン酸メチル、酢酸−２，２，２−トリフルオロエチル、リン酸トリス（２，２−ジフルオロエチル）、リン酸トリス（２，２，２−トリフルオロエチル）等を挙げることができる。
Examples of the ester include
上記エーテルとしては、例えば１，１，２，２−テトラフルオロエチル−２，２，２−トリフルオロエチルエーテル、メチルヘプタフルオロプロピルエーテル、メチルノナフルオロブチルエーテル等を挙げることができる。 Examples of the ether include 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, methylheptafluoropropyl ether, methylnonafluorobutyl ether and the like.
フッ素化カーボネート以外の有機溶媒としては、非水電解質の粘度を低く抑えることができる観点から、フッ素化鎖状カーボネート以外の鎖状カーボネートが好ましい。 As the organic solvent other than the fluorinated carbonate, a chain carbonate other than the fluorinated chain carbonate is preferable from the viewpoint that the viscosity of the non-aqueous electrolyte can be kept low.
上記非水溶媒における上記フッ素化カーボネートの含有量の下限としては、１０体積％が好ましく、３０体積％がより好ましい。上記フッ素化カーボネートの含有量の上限としては、１００体積％が好ましく、５０体積％がより好ましい。上記非水溶媒における上記フッ素化カーボネートの含有量が上記範囲であることで、当該非水電解質蓄電素子のデンドライトの形成に対する抑制効果をより高めることができる。 The lower limit of the content of the fluorinated carbonate in the non-aqueous solvent is preferably 10% by volume, more preferably 30% by volume. The upper limit of the content of the fluorinated carbonate is preferably 100% by volume, more preferably 50% by volume. When the content of the fluorinated carbonate in the non-aqueous solvent is in the above range, the effect of suppressing the formation of dendrites of the non-aqueous electrolyte power storage element can be further enhanced.
上記非水溶媒における上記フッ素化環状カーボネートの含有量の下限としては、１０体積％が好ましく、２０体積％がより好ましい。上記フッ素化環状カーボネートの含有量の上限としては、５０体積％が好ましく、４０体積％がより好ましい。上記非水溶媒における上記フッ素化環状カーボネートの含有量が上記範囲であることで、当該非水電解質蓄電素子のデンドライトの形成に対する抑制効果をより高めることができる。また、リチウム金属上で非水電解質が連続的に還元分解されることが抑制され、分解生成物であるガスの発生量が低減される。 The lower limit of the content of the fluorinated cyclic carbonate in the non-aqueous solvent is preferably 10% by volume, more preferably 20% by volume. The upper limit of the content of the fluorinated cyclic carbonate is preferably 50% by volume, more preferably 40% by volume. When the content of the fluorinated cyclic carbonate in the non-aqueous solvent is in the above range, the effect of suppressing the formation of dendrites of the non-aqueous electrolyte power storage device can be further enhanced. In addition, the continuous reduction decomposition of the non-aqueous electrolyte on the lithium metal is suppressed, and the amount of gas, which is a decomposition product, is reduced.
上記非水溶媒におけるフッ素化溶媒の含有量の下限としては、５０体積％が好ましく、７０体積％がより好ましく、９０体積％がさらに好ましく、９９体積％がさらに好ましい。全非水溶媒におけるフッ素化溶媒の含有量は１００体積％であることが特に好ましい。非水溶媒を実質的にフッ素化溶媒のみから構成することで、非水電解質の耐酸化性をより高めることなどができる。なお、フッ素化溶媒とは、フッ素化カーボネート（フッ素化鎖状カーボネート及びフッ素化環状カーボネート）を含み、フッ素化エステル、フッ素化エーテル等、分子内にフッ素原子を有する非水溶媒をいう。 The lower limit of the content of the fluorinated solvent in the non-aqueous solvent is preferably 50% by volume, more preferably 70% by volume, further preferably 90% by volume, still more preferably 99% by volume. The content of the fluorinated solvent in the total non-aqueous solvent is particularly preferably 100% by volume. By substantially composing the non-aqueous solvent only from the fluorinated solvent, the oxidation resistance of the non-aqueous electrolyte can be further enhanced. The fluorinated solvent includes a fluorinated carbonate (fluorinated chain carbonate and fluorinated cyclic carbonate), and refers to a non-aqueous solvent having a fluorine atom in the molecule, such as a fluorinated ester and a fluorinated ether.
（電解質塩）
上記電解質塩としては、一般的な非水電解質の電解質塩として通常用いられる公知の電解質塩を用いることができる。上記電解質塩としては、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、オニウム塩等を挙げることができるが、リチウム塩が好ましい。
(Electrolyte salt)
As the electrolyte salt, a known electrolyte salt usually used as an electrolyte salt of a general non-aqueous electrolyte can be used. Examples of the electrolyte salt include lithium salt, sodium salt, potassium salt, magnesium salt, onium salt and the like, but lithium salt is preferable.
上記リチウム塩としては、ＬｉＰＦ６、ＬｉＰＯ２Ｆ２、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＳＯ２Ｆ）２等の無機リチウム塩、ＬｉＳＯ３ＣＦ３、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２、ＬｉＮ（ＳＯ２ＣＦ３）（ＳＯ２Ｃ４Ｆ９）、ＬｉＣ（ＳＯ２ＣＦ３）３、ＬｉＣ（ＳＯ２Ｃ２Ｆ５）３等のフッ化炭化水素基を有するリチウム塩などを挙げることができる。これらの中でも、無機リチウム塩が好ましく、ＬｉＰＦ６がより好ましい。 Examples of the lithium salt include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , and LiN (SO). 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiC (SO 2 C 2 F 5 ) 3 and other fluorinated hydrocarbon groups Can be mentioned, such as a lithium salt having. Among these, an inorganic lithium salt is preferable, and LiPF 6 is more preferable.
上記非水電解質における上記電解質塩の含有量の下限としては、０．１ｍｏｌ ｄｍ−３が好ましく、０．３ｍｏｌ ｄｍ−３がより好ましく、０．５ｍｏｌ ｄｍ−３がさらに好ましい。一方、この上限としては、特に限定されないが、３ｍｏｌ ｄｍ−３が好ましく、２ｍｏｌ ｄｍ−３がより好ましい。 As the lower limit of the content of the electrolyte salt in the non-aqueous electrolyte, 0.1 mol dm -3 is preferable, 0.3 mol dm -3 is more preferable, and 0.5 mol dm -3 is further preferable. On the other hand, the upper limit is not particularly limited, but 3 mol dm -3 is preferable, and 2 mol dm -3 is more preferable.
（その他の添加剤等）
上記非水電解質は、本発明の効果を阻害しない限り、その他の添加剤を含有していてもよい。上記その他の添加剤としては、一般的な非水電解質に含有される各種添加剤を挙げることができる。上記その他の添加剤としては、例えばビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、ｔ−ブチルベンゼン、ｔ−アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物；２−フルオロビフェニル、ｏ−シクロヘキシルフルオロベンゼン、ｐ−シクロヘキシルフルオロベンゼン等の上記芳香族化合物の部分ハロゲン化物；２，４−ジフルオロアニソール、２，５−ジフルオロアニソール、２，６−ジフルオロアニソール、３，５−ジフルオロアニソール等のハロゲン化アニソール化合物；無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸、無水グルタコン酸、無水イタコン酸、シクロヘキサンジカルボン酸無水物；亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、４，４’−ビス（２，２−ジオキソ−１，３，２−ジオキサチオラン）、４−メチルスルホニルオキシメチル−２，２−ジオキソ−１，３，２−ジオキサチオラン、チオアニソール、ジフェニルジスルフィド、ジピリジニウムジスルフィド、パーフルオロオクタン、ホウ酸トリストリメチルシリル、リン酸トリストリメチルシリル、チタン酸テトラキストリメチルシリル等が挙げられる。これら添加剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
(Other additives, etc.)
The non-aqueous electrolyte may contain other additives as long as the effects of the present invention are not impaired. Examples of the other additives include various additives contained in a general non-aqueous electrolyte. Examples of the other additives include biphenyl, alkyl biphenyl, terphenyl, a partially hydride of turphenyl, and aromatic compounds such as cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; 2-fluoro. Partial halides of the above aromatic compounds such as biphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5-difluoro Halogenated anisole compounds such as anisole; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfite, dimethyl sulfate, Ethylene Sulfate, Sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, 4,4'-bis (2,2-dioxo-1,3,2-dioxathiolane), 4-methylsulfonyl Examples thereof include oxymethyl-2,2-dioxo-1,3,2-dioxathiolane, thioanisole, diphenyldisulfide, dipyridinium disulfide, perfluorooctane, tristrimethylsilyl borate, tristrimethylsilyl phosphate, tetrakistrimethylsilyl titanate and the like. These additives may be used alone or in combination of two or more.
非水電解質に含まれる添加剤の含有量は、非水電解質全体に対して０．０１質量％以上１０質量％以下が好ましく、０．１質量％以上７質量％以下がより好ましく、０．２質量％以上５質量％以下がさらに好ましく、０．３質量％以上３質量％以下が特に好ましい。添加剤の含有量を上記の範囲とすることで、高温保存後の容量維持性能又は充放電サイクル性能を向上させたり、安全性をより向上させたりすることができる。 The content of the additive contained in the non-aqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, and 0.2. More preferably, it is more preferably mass% or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and 3% by mass or less. By setting the content of the additive in the above range, it is possible to improve the capacity maintenance performance or charge / discharge cycle performance after high temperature storage, and further improve the safety.
上記非水電解質は、通常、上記非水溶媒に、上記電解質塩等の各成分を添加し、溶解させることにより得ることができる。 The non-aqueous electrolyte can usually be obtained by adding and dissolving each component such as the electrolyte salt to the non-aqueous solvent.
［セパレータ］
セパレータは、上記負極活物質層及び上記正極活物質層間に介在する。セパレータの形態としては、例えば、織布、不織布、多孔質樹脂フィルム等が挙げられ、多孔質樹脂フィルムが好ましい。セパレータの材料は、通常、樹脂である。セパレータの材料となる樹脂としては、シャットダウン機能の観点から例えばポリエチレン、ポリプロピレン等のポリオレフィンが好ましく、耐酸化分解性の観点から例えばポリイミドやアラミド等が好ましい。セパレータとして、これらの樹脂を複合した材料を用いてもよい。
[Separator]
The separator is interposed between the negative electrode active material layer and the positive electrode active material layer. Examples of the form of the separator include a woven fabric, a non-woven fabric, a porous resin film, and the like, and a porous resin film is preferable. The material of the separator is usually a resin. As the resin used as the material of the separator, polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of shutdown function, and polyimide and aramid are preferable from the viewpoint of oxidative decomposition resistance. As the separator, a material in which these resins are combined may be used.
セパレータの平均厚さとしては、例えば３μｍ以上５０μｍ以下が好ましく、６μｍ以上２５μｍ以下がより好ましい。セパレータの平均厚さが上記下限以上であることで、短絡の発生をより抑制することができる。一方、セパレータの平均厚さが上記上限以下であることで、非水電解質蓄電素子の高エネルギー密度化を図ることができる。なお、セパレータの平均厚さは、任意の１０カ所で測定した厚さの平均値とする。 The average thickness of the separator is, for example, preferably 3 μm or more and 50 μm or less, and more preferably 6 μm or more and 25 μm or less. When the average thickness of the separator is at least the above lower limit, the occurrence of a short circuit can be further suppressed. On the other hand, when the average thickness of the separator is not more than the above upper limit, it is possible to increase the energy density of the non-aqueous electrolyte power storage element. The average thickness of the separator shall be the average value of the thickness measured at any 10 locations.
［無機粒子層］
第１無機粒子層は、上記セパレータ及び上記負極活物質層間に介在する。第１無機粒子層は無機粒子を含む多孔質の層である。第１無機粒子層はバインダー等のその他の成分が含有されていてもよい。第１無機粒子層の形態としては、第１無機粒子層が上記セパレータの表面に一体的に形成されていてもよく、第１無機粒子層が負極活物質層の表面上に形成されていてもよい。上記負極活物質層及び上記セパレータ間に第１無機粒子層が介在することで、リチウム金属の体積変化に起因する圧迫によるセパレータの細孔の閉塞に対する耐性が高まる。このため、リチウム金属とセパレータとの界面における電流分布が均一に維持されるので、デンドライトの形成が抑制される。このように、当該非水電解質蓄電素子はデンドライトの形成に対する抑制効果に優れる結果、短絡発生に対する抑制効果が高い。
[Inorganic particle layer]
The first inorganic particle layer is interposed between the separator and the negative electrode active material layer. The first inorganic particle layer is a porous layer containing inorganic particles. The first inorganic particle layer may contain other components such as a binder. As the form of the first inorganic particle layer, the first inorganic particle layer may be integrally formed on the surface of the separator, or the first inorganic particle layer may be formed on the surface of the negative electrode active material layer. good. By interposing the first inorganic particle layer between the negative electrode active material layer and the separator, the resistance to the blockage of the pores of the separator due to the compression caused by the volume change of the lithium metal is enhanced. Therefore, the current distribution at the interface between the lithium metal and the separator is maintained uniformly, and the formation of dendrites is suppressed. As described above, the non-aqueous electrolyte power storage element is excellent in suppressing the formation of dendrites, and as a result, is highly effective in suppressing the occurrence of short circuits.
上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することが好ましい。第２無機粒子層は、上記第１無機粒子層と同様の構成を有する。また、第２無機粒子層の形態としては、第２無機粒子層が上記セパレータの表面に一体的に形成されていてもよく、第２無機粒子層が正極活物質層の表面上に形成されていてもよい。上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することで、長期の充放電サイクル時の正極活物質層表面における非水電解質の分解生成物によるセパレータの目詰まりなどが、多孔質の第２無機粒子層によって抑制される。その結果、正極とセパレータとの界面における電流分布が均一に維持されると考えられる。従って、上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有することで、短絡の発生に対する抑制効果をより向上できる。 It is preferable to further have a second inorganic particle layer interposed between the separator and the positive electrode active material layer. The second inorganic particle layer has the same structure as the first inorganic particle layer. Further, as the form of the second inorganic particle layer, the second inorganic particle layer may be integrally formed on the surface of the separator, and the second inorganic particle layer is formed on the surface of the positive electrode active material layer. You may. By further having the second inorganic particle layer interposed between the separator and the positive electrode active material layer, clogging of the separator due to the decomposition product of the non-aqueous electrolyte on the surface of the positive electrode active material layer during a long-term charge / discharge cycle can be prevented. It is suppressed by the porous second inorganic particle layer. As a result, it is considered that the current distribution at the interface between the positive electrode and the separator is maintained uniformly. Therefore, by further having the second inorganic particle layer interposed between the separator and the positive electrode active material layer, the effect of suppressing the occurrence of a short circuit can be further improved.
無機粒子を構成する材料の具体的種類としては、酸化鉄、酸化ケイ素、酸化アルミニウム、酸化チタン、チタン酸バリウム、酸化ジルコニウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の酸化物；水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物；窒化アルミニウム、窒化ケイ素等の窒化物；炭酸カルシウム等の炭酸塩；硫酸バリウム等の硫酸塩；フッ化カルシウム、フッ化バリウム等の難溶性のイオン結晶；シリコン、ダイヤモンド等の共有結合性結晶；タルク、モンモリロナイト、ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。無機粒子としては、軽量化の観点からこれらの中でもより密度の低いものが好ましい。無機粒子として、これらの物質の単体又は複合体を単独で用いてもよく、２種以上を混合して用いてもよい。 Specific types of materials constituting the inorganic particles include oxidation of iron oxide, silicon oxide, aluminum oxide, titanium oxide, barium titanate, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, aluminosilicate and the like. Substances; Hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide; Nitridees such as aluminum nitride and silicon nitride; Carbonates such as calcium carbonate; Sulfates such as barium sulfate; Calcium fluoride, barium fluoride Poorly soluble ion crystals such as; covalent crystals such as silicon and diamond; substances derived from mineral resources such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mulite, spinel, olivine, cericite, bentonite, mica, etc. Artificial products, etc. As the inorganic particles, those having a lower density are preferable from the viewpoint of weight reduction. As the inorganic particles, simple substances or complexes of these substances may be used alone, or two or more kinds thereof may be mixed and used.
上記無機粒子層における無機粒子の含有量としては、５０質量％以上１００質量％以下が好ましく、６０質量％以上９９質量％以下がより好ましく、７０質量％以上９８質量％以下がさらに好ましい。 The content of the inorganic particles in the inorganic particle layer is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 99% by mass or less, and further preferably 70% by mass or more and 98% by mass or less.
上記無機粒子層がバインダーを含有する場合、上記無機粒子層におけるバインダーの含有量としては、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましい。 When the inorganic particle layer contains a binder, the content of the binder in the inorganic particle layer is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.
上記無機粒子の平均粒径の上限としては、１０μｍが好ましく、８μｍがより好ましく、５μｍがさらに好ましい。上記平均粒径の下限としては特に限定されないが、例えば５ｎｍ又は５０ｎｍであってよく、５００ｎｍであってもよい。また、上記無機粒子は、小粒径のほうが大粒径と比較して無機層の面積あたりの細孔の数が増加することで電流分布がより均一となることから、本発明の効果をより奏することができる。ここで、「平均粒径」とは、ＪＩＳ−Ｚ−８８２５（２０１３年）に準拠し、粒子を溶媒で希釈した希釈液に対しレーザ回折・散乱法により測定した粒径分布に基づき、ＪＩＳ−Ｚ−８８１９−２（２００１年）に準拠し計算される体積基準積算分布が５０％となる値を意味する。 The upper limit of the average particle size of the inorganic particles is preferably 10 μm, more preferably 8 μm, and even more preferably 5 μm. The lower limit of the average particle size is not particularly limited, but may be, for example, 5 nm or 50 nm, or 500 nm. Further, in the above-mentioned inorganic particles, the current distribution becomes more uniform by increasing the number of pores per area of the inorganic layer in the case of the small particle size as compared with the case of the large particle size, so that the effect of the present invention can be further enhanced. Can play. Here, the "average particle size" is based on JIS-Z-8825 (2013), and is based on the particle size distribution measured by the laser diffraction / scattering method for a diluted solution obtained by diluting the particles with a solvent. It means a value at which the volume-based integrated distribution calculated in accordance with Z-8819-2 (2001) is 50%.
無機粒子層のバインダーとしては、上記正極活物質層のバインダーと同様のものを用いることができる。 As the binder of the inorganic particle layer, the same binder as that of the positive electrode active material layer can be used.
無機粒子層の平均厚さとしては、例えば２μｍ以上１０μｍ以下が好ましく、３μｍ以上６μｍ以下がより好ましい。無機粒子層の平均厚さが上記下限以上であることで、短絡の発生をより抑制することができる。一方、無機粒子層の平均厚さが上記上限以下であることで、高いエネルギー密度を維持することができる。なお、無機粒子層の平均厚さは、任意の１０カ所で測定した厚さの平均値とする。 The average thickness of the inorganic particle layer is, for example, preferably 2 μm or more and 10 μm or less, and more preferably 3 μm or more and 6 μm or less. When the average thickness of the inorganic particle layer is at least the above lower limit, the occurrence of a short circuit can be further suppressed. On the other hand, when the average thickness of the inorganic particle layer is not more than the above upper limit, high energy density can be maintained. The average thickness of the inorganic particle layer is the average value of the thickness measured at any 10 locations.
セパレータ及び無機粒子層全体の平均厚さとしては、例えば５μｍ以上６０μｍ以下が好ましく、９μｍ以上３０μｍ以下がより好ましい。セパレータ及び無機粒子層全体の平均厚さが上記下限以上であることで、短絡の発生をより抑制することができる。一方、セパレータ及び無機粒子層全体の平均厚さが上記上限以下であることで、非水電解質蓄電素子の高エネルギー密度化を図ることができる。なお、セパレータ及び無機粒子層全体の平均厚さは、任意の１０カ所で測定した厚さの平均値とする。 The average thickness of the separator and the entire inorganic particle layer is, for example, preferably 5 μm or more and 60 μm or less, and more preferably 9 μm or more and 30 μm or less. When the average thickness of the separator and the entire inorganic particle layer is at least the above lower limit, the occurrence of a short circuit can be further suppressed. On the other hand, when the average thickness of the separator and the entire inorganic particle layer is not more than the above upper limit, it is possible to increase the energy density of the non-aqueous electrolyte power storage element. The average thickness of the separator and the entire inorganic particle layer shall be the average value of the thickness measured at any 10 locations.
［非水電解質蓄電素子の具体的構成］
本実施形態の非水電解質蓄電素子の形状については特に限定されるものではなく、例えば、円筒型電池、パウチフィルム型電池、角型電池、扁平型電池、コイン型電池、ボタン型電池等が挙げられる。
[Specific configuration of non-aqueous electrolyte power storage element]
The shape of the non-aqueous electrolyte power storage element of the present embodiment is not particularly limited, and examples thereof include a cylindrical battery, a pouch film type battery, a square battery, a flat type battery, a coin type battery, and a button type battery. Be done.
図１に非水電解質蓄電素子１として、角型の非水電解質二次電池を一例として示す。なお、同図は、ケース内部を透視した図としている。セパレータを挟んで巻回された正極及び負極を有する電極体２が角型のケース３に収納される。正極は正極リード４１を介して正極端子４と電気的に接続されている。負極は負極リード５１を介して負極端子５と電気的に接続されている。
FIG. 1 shows, as an example, a square non-aqueous electrolyte secondary battery as the non-aqueous electrolyte power storage element 1. The figure is a perspective view of the inside of the case. The
［非水電解質蓄電素子の製造方法］
本実施に係る非水電解質蓄電素子の製造方法は、公知の方法から適宜選択できる。当該製造方法は、例えば電極体を準備する工程と、非水電解質を準備する工程と、電極体及び非水電解質をケースに収容する工程と、を備える。電極体を準備する工程は、正極及び負極を準備する工程と、正極及び負極を、セパレータを介して積層又は巻回することにより電極体を形成する工程を備える。
[Manufacturing method of non-aqueous electrolyte power storage element]
The method for manufacturing the non-aqueous electrolyte power storage element according to this embodiment can be appropriately selected from known methods. The manufacturing method includes, for example, a step of preparing an electrode body, a step of preparing a non-aqueous electrolyte, and a step of accommodating the electrode body and the non-aqueous electrolyte in a case. The step of preparing the electrode body includes a step of preparing a positive electrode and a negative electrode, and a step of forming the electrode body by laminating or winding the positive electrode and the negative electrode via a separator.
上記非水電解質をケースに収容する工程では、公知の方法から適宜選択できる。例えば、液状の非水電解質（「電解液」ともいう）を用いる場合、ケースに形成された注入口から電解液を注入した後、注入口を封止すればよい。当該製造方法によって得られる非水電解質蓄電素子を構成する各要素についての詳細は上述したとおりである。 In the step of accommodating the non-aqueous electrolyte in the case, a known method can be appropriately selected. For example, when a liquid non-aqueous electrolyte (also referred to as “electrolyte solution”) is used, the injection port may be sealed after the electrolyte solution is injected from the injection port formed in the case. The details of each element constituting the non-aqueous electrolyte power storage element obtained by the manufacturing method are as described above.
［その他の実施形態］
なお、本発明に係る非水電解質蓄電素子は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加えてもよい。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成又は周知技術に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。また、ある実施形態の構成に対して周知技術を付加することができる。
[Other embodiments]
The non-aqueous electrolyte power storage device according to the present invention is not limited to the above embodiment, and various modifications may be made without departing from the gist of the present invention. For example, the configuration of one embodiment can be added to the configuration of another embodiment, and a part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a well-known technique. In addition, some of the configurations of certain embodiments can be deleted. Further, a well-known technique can be added to the configuration of a certain embodiment.
上記実施の形態においては、非水電解質蓄電素子が非水電解質二次電池である形態を中心に説明したが、その他の非水電解質蓄電素子であってもよい。その他の非水電解質蓄電素子としては、キャパシタ（電気二重層キャパシタ、リチウムイオンキャパシタ）等が挙げられる。非水電解質二次電池としては、リチウムイオン非水電解質二次電池が挙げられる。 In the above embodiment, the non-aqueous electrolyte power storage element has been described mainly in the form of a non-water electrolyte secondary battery, but other non-water electrolyte power storage elements may be used. Examples of other non-aqueous electrolyte storage elements include capacitors (electric double layer capacitors, lithium ion capacitors) and the like. Examples of the non-aqueous electrolyte secondary battery include a lithium ion non-aqueous electrolyte secondary battery.
本発明は、上記の非水電解質蓄電素子を複数備える蓄電装置としても実現することができる。また、本発明の非水電解質蓄電素子（セル）を単数又は複数個用いることにより蓄電ユニットを構成することができ、さらにこの蓄電ユニットを用いて蓄電装置を構成することができる。上記蓄電装置は、電気自動車（ＥＶ）、ハイブリッド自動車（ＨＥＶ）、プラグインハイブリッド自動車（ＰＨＥＶ）等の自動車用電源として用いることができる。さらに、上記蓄電装置は、エンジン始動用電源装置、補機用電源装置、無停電電源装置（ＵＰＳ）等の種々の電源装置に用いることができる。 The present invention can also be realized as a power storage device including a plurality of the above-mentioned non-aqueous electrolyte power storage elements. Further, a power storage unit can be configured by using a single or a plurality of non-aqueous electrolyte power storage elements (cells) of the present invention, and a power storage device can be further configured by using the power storage unit. The power storage device can be used as a power source for automobiles such as electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid vehicles (PHEVs). Further, the power storage device can be used for various power supply devices such as an engine starting power supply device, an auxiliary power supply device, and an uninterruptible power supply (UPS).
図２に、電気的に接続された二以上の非水電解質蓄電素子１が集合した蓄電ユニット２０をさらに集合させた蓄電装置３０の一例を示す。蓄電装置３０は、二以上の非水電解質蓄電素子１を電気的に接続するバスバ（図示せず）、二以上の蓄電ユニット２０を電気的に接続するバスバ（図示せず）を備えていてもよい。蓄電ユニット２０又は蓄電装置３０は、一以上の非水電解質蓄電素子の状態を監視する状態監視装置（図示せず）を備えていてもよい。
FIG. 2 shows an example of a
以下、実施例によって本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
［実施例１］
（正極の作製）
正極活物質として、α―ＮａＦｅＯ２型結晶構造を有し、Ｌｉ１＋αＭｅ１−αＯ２（Ｍｅは遷移金属）で表されるリチウム遷移金属複合酸化物を用いた。ここで、ＬｉとＭｅのモル比Ｌｉ／Ｍｅは１．３３であり、Ｍｅは、Ｎｉ及びＭｎからなり、Ｎｉ：Ｍｎ＝１：２のモル比で含んでいるものであった。
[Example 1]
(Preparation of positive electrode)
As the positive electrode active material, a lithium transition metal composite oxide having an α-NaFeO type 2 crystal structure and represented by Li 1 + α Me 1-α O 2 (Me is a transition metal) was used. Here, the molar ratio Li / Me of Li and Me was 1.33, and Me consisted of Ni and Mn and contained Ni: Mn = 1: 2.
Ｎ−メチルピロリドン（ＮＭＰ）を分散媒とし、上記正極活物質、導電剤であるアセチレンブラック（ＡＢ）、及びバインダーであるポリフッ化ビニリデン（ＰＶＤＦ）を９４：４．５：１．５の質量比率で含有する正極ペーストを作製した。正極基材である平均厚さ２０μｍのアルミニウム箔の片面に、上記正極ペーストを塗布し、乾燥し、プレス後、切断し、幅３０ｍｍ、長さ４０ｍｍの矩形状に正極活物質層が配置された正極を作製した。 Using N-methylpyrrolidone (NMP) as a dispersion medium, the positive electrode active material, acetylene black (AB) as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder have a mass ratio of 94: 4.5: 1.5. The positive electrode paste contained in the above was prepared. The positive electrode paste was applied to one side of an aluminum foil having an average thickness of 20 μm, which is a positive electrode base material, dried, pressed, and cut, and a positive electrode active material layer was arranged in a rectangular shape having a width of 30 mm and a length of 40 mm. A positive electrode was prepared.
（負極の作製）
負極基材である平均厚さ１０μｍの銅箔の片面に、負極活物質層として平均厚さ６０μｍのリチウム金属箔（リチウム金属１００質量％）を積層し、プレス後、幅３２ｍｍ、長さ４２ｍｍの矩形状に切断することで、負極を作製した。
(Manufacturing of negative electrode)
A lithium metal foil (100% by mass of lithium metal) having an average thickness of 60 μm is laminated as a negative electrode active material layer on one side of a copper foil having an average thickness of 10 μm, which is a negative electrode base material. A negative electrode was produced by cutting into a rectangular shape.
（非水電解質の調製）
フルオロエチレンカーボネート（ＦＥＣ）及び２，２，２−トリフルオロエチルメチルカーボネート（ＴＦＥＭＣ）を３０：７０の体積比で混合した混合溶媒にＬｉＰＦ６を１ｍｏｌ／ｄｍ３の濃度で溶解させ、非水電解質とした。
(Preparation of non-aqueous electrolyte)
LiPF 6 was dissolved in a mixed solvent of fluoroethylene carbonate (FEC) and 2,2,2-trifluoroethylmethyl carbonate (TFEMC) in a volume ratio of 30:70 at a concentration of 1 mol / dm 3 , and a non-aqueous electrolyte was added. And said.
（セパレータ及び無機粒子層）
セパレータとしては、ポリオレフィン系樹脂のみからなる平均厚さ１５μｍのものを用いた。また、第１無機粒子層及び第２無機粒子層はそれぞれ上記セパレータの表面に一体的に形成し、第１無機粒子層がセパレータ及び負極活物質層間に介在し、第２無機粒子層がセパレータ及び正極活物質層間に介在するように配置した。第１無機粒子層及び第２無機粒子層は、それぞれ平均厚さ６μｍであり、無機粒子とバインダーとを質量比で９５：５となるように含有させた。無機粒子としては、アルミノケイ酸塩を用いた。
(Separator and inorganic particle layer)
As the separator, a separator having an average thickness of 15 μm made of only a polyolefin resin was used. Further, the first inorganic particle layer and the second inorganic particle layer are integrally formed on the surface of the separator, the first inorganic particle layer is interposed between the separator and the negative electrode active material layer, and the second inorganic particle layer is the separator and the separator. It was arranged so as to intervene between the layers of the positive electrode active material. The first inorganic particle layer and the second inorganic particle layer each had an average thickness of 6 μm, and contained the inorganic particles and the binder in a mass ratio of 95: 5. Aluminosilicate was used as the inorganic particles.
（非水電解質蓄電素子の作製）
上記セパレータ及び無機粒子層を介して、上記正極と上記負極とを積層することにより電極体を作製した。この電極体をケースに収納し、内部に上記非水電解質を注入した後、封口し、実施例１の非水電解質蓄電素子（二次電池）を得た。
(Manufacturing of non-aqueous electrolyte power storage element)
An electrode body was produced by laminating the positive electrode and the negative electrode via the separator and the inorganic particle layer. The electrode body was housed in a case, the non-aqueous electrolyte was injected into the case, and then the electrode body was sealed to obtain the non-aqueous electrolyte power storage element (secondary battery) of Example 1.
［実施例２から実施例６及び比較例１から比較例４］
無機粒子層の構成及び非水電解質の非水溶媒の組成を表１に示すとおりとしたこと以外は、実施例１と同様にして、実施例２から実施例６及び比較例１から比較例４の非水電解質蓄電素子を得た。
[Examples 2 to 6 and Comparative Examples 1 to 4]
Examples 2 to 6 and Comparative Examples 1 to 4 are the same as in Example 1 except that the composition of the inorganic particle layer and the composition of the non-aqueous solvent of the non-aqueous electrolyte are as shown in Table 1. The non-aqueous electrolyte power storage element of the above was obtained.
（初期充放電）
得られた各非水電解質蓄電素子について、以下の条件にて初期充放電を行った。２５℃において、充電電流０．１Ｃ、充電終止電圧４．６Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０２Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電を２サイクル行った。
(Initial charge / discharge)
Each of the obtained non-aqueous electrolyte power storage elements was initially charged and discharged under the following conditions. At 25 ° C., constant current and constant voltage charging was performed with a charging current of 0.1 C and a charge termination voltage of 4.6 V. The charging end condition was set until the charging current reached 0.02C. After that, a rest period of 10 minutes was provided. Then, a constant current discharge was performed with a discharge current of 0.1 C and a discharge end voltage of 2.0 V, and then a rest period of 10 minutes was provided. This charge / discharge was performed for 2 cycles.
（充放電サイクル試験）
次いで、以下の充放電サイクル試験を行った。２５℃において、充電電流０．２Ｃ、充電終止電圧４．６Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０５Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電のサイクルを繰り返し、短絡が生じるまでのサイクル数を記録した。結果を表１に示す。なお、「−」は該当する成分を含まないことを意味する。
(Charge / discharge cycle test)
Then, the following charge / discharge cycle test was performed. At 25 ° C., constant current and constant voltage charging was performed with a charging current of 0.2 C and a charge termination voltage of 4.6 V. The charging end condition was set until the charging current reached 0.05 C. After that, a rest period of 10 minutes was provided. Then, a constant current discharge was performed with a discharge current of 0.1 C and a discharge end voltage of 2.0 V, and then a rest period of 10 minutes was provided. This charge / discharge cycle was repeated, and the number of cycles until a short circuit occurred was recorded. The results are shown in Table 1. In addition, "-" means that the corresponding component is not included.
表１に示されるように、セパレータ及び負極活物質層間に介在する第１無機粒子層を備え、非水溶媒がフッ素化カーボネートを含む実施例１から実施例６の非水電解質蓄電素子においては、短絡が生じるまでのサイクル数が５０回を超え、短絡の発生が十分に抑制された結果となった。また、上記セパレータ及び上記正極活物質層間に介在する第２無機粒子層をさらに有する実施例１及び実施例３から実施例６は、セパレータ及び負極活物質層間に介在する第１無機粒子層のみを備える実施例２よりも短絡の発生に対する抑制効果がより高い結果となった。
一方、セパレータ及び負極活物質層間に介在する第１無機粒子層を備えていない比較例１、比較例３及び比較例４、並びに上記第１無機粒子層を備えているが非水溶媒がフッ素化カーボネートを含まない比較例２は、短絡の発生に対する抑制効果が低い結果となった。
As shown in Table 1, in the non-aqueous electrolyte power storage elements of Examples 1 to 6, which are provided with a first inorganic particle layer interposed between the separator and the negative electrode active material layer and the non-aqueous solvent contains a fluorinated carbonate. The number of cycles until the short circuit occurred exceeded 50 times, and the result was that the occurrence of the short circuit was sufficiently suppressed. Further, in Examples 1 and 3 to 6 having a second inorganic particle layer interposed between the separator and the positive electrode active material layer, only the first inorganic particle layer interposed between the separator and the negative electrode active material layer is used. The result was that the effect of suppressing the occurrence of a short circuit was higher than that of the second embodiment provided.
On the other hand, Comparative Example 1, Comparative Example 3 and Comparative Example 4 having no first inorganic particle layer interposed between the separator and the negative electrode active material layer, and the first inorganic particle layer having the above-mentioned first inorganic particle layer, but the non-aqueous solvent was fluorinated. Comparative Example 2 containing no carbonate had a low inhibitory effect on the occurrence of a short circuit.
以上の結果、当該非水電解質蓄電素子は、短絡の発生に対する抑制効果が高いことが示された。 As a result of the above, it was shown that the non-aqueous electrolyte power storage element has a high effect of suppressing the occurrence of a short circuit.
本発明は、パーソナルコンピュータ、通信端末等の電子機器、自動車等の電源として使用される非水電解質蓄電素子に適用できる。 The present invention can be applied to a non-aqueous electrolyte power storage element used as a power source for personal computers, electronic devices such as communication terminals, automobiles and the like.
１ 非水電解質蓄電素子
２ 電極体
３ ケース
４ 正極端子
４１ 正極リード
５ 負極端子
５１ 負極リード
２０ 蓄電ユニット
３０ 蓄電装置
1 Non-aqueous electrolyte
Claims (4)
正極活物質層を有する正極と、
非水溶媒を含有する非水電解質と、
上記負極活物質層及び上記正極活物質層間に介在するセパレータと、
上記セパレータ及び上記負極活物質層間に介在する第１無機粒子層と
を備え、
上記負極活物質層がリチウム金属を含み、
上記非水溶媒がフッ素化カーボネートを含む非水電解質蓄電素子。 A negative electrode having a negative electrode active material layer and a negative electrode
A positive electrode having a positive electrode active material layer and a positive electrode
A non-aqueous electrolyte containing a non-aqueous solvent and
A separator interposed between the negative electrode active material layer and the positive electrode active material layer,
The separator and the first inorganic particle layer interposed between the negative electrode active material layers are provided.
The negative electrode active material layer contains lithium metal and contains
A non-aqueous electrolyte storage device in which the non-aqueous solvent contains a fluorinated carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020091276A JP2021190184A (en) | 2020-05-26 | 2020-05-26 | Non-aqueous electrolyte power storage element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020091276A JP2021190184A (en) | 2020-05-26 | 2020-05-26 | Non-aqueous electrolyte power storage element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021190184A true JP2021190184A (en) | 2021-12-13 |
Family
ID=78849999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020091276A Pending JP2021190184A (en) | 2020-05-26 | 2020-05-26 | Non-aqueous electrolyte power storage element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021190184A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102550803B1 (en) * | 2022-12-01 | 2023-07-04 | 한국세라믹기술원 | Separator for electrochemical device with improved lifespan property and manufacturing method thereof and electrochemical device including the same |
-
2020
- 2020-05-26 JP JP2020091276A patent/JP2021190184A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102550803B1 (en) * | 2022-12-01 | 2023-07-04 | 한국세라믹기술원 | Separator for electrochemical device with improved lifespan property and manufacturing method thereof and electrochemical device including the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6911655B2 (en) | A method for manufacturing a non-aqueous electrolyte for a power storage element, a non-aqueous electrolyte power storage element, and a non-aqueous electrolyte power storage element. | |
| JP2021190184A (en) | Non-aqueous electrolyte power storage element | |
| JP7411161B2 (en) | Energy storage element | |
| JP7409132B2 (en) | Nonaqueous electrolyte storage element | |
| JP7371396B2 (en) | Non-aqueous electrolyte secondary battery and method for manufacturing non-aqueous electrolyte secondary battery | |
| JP2022011572A (en) | Nonaqueous electrolyte power storage device, and manufacturing method thereof | |
| JP2021190165A (en) | Positive electrode and power storage element | |
| JP2020173998A (en) | Non-aqueous electrolyte storage element and manufacturing method thereof | |
| EP4030521A1 (en) | Non-aqueous electrolyte power storage element and power storage device | |
| WO2023224071A1 (en) | Nonaqueous electrolyte power storage element | |
| EP4307405A1 (en) | Nonaqueous-electrolyte electricity storage element | |
| WO2022181516A1 (en) | Nonaqueous electrolyte power storage element | |
| WO2023248769A1 (en) | Active material particles, electrode, power storage element and power storage device | |
| EP4250419A1 (en) | Nonaqueous electrolyte power storage element, electronic device, and automobile | |
| WO2021241467A1 (en) | Non-aqueous electrolytic solution power storage element | |
| WO2023100801A1 (en) | Nonaqueous electrolyte power storage element, device, and method for using nonaqueous electrolyte power storage element | |
| WO2022239520A1 (en) | Power storage element, manufacturing method therefor, and power storage device | |
| WO2023171796A1 (en) | Negative electrode, power storage element, and power storage device | |
| WO2023224070A1 (en) | Non-aqueous electrolyte power storage element | |
| WO2022163125A1 (en) | Nonaqueous electrolyte power storage element, power storage device, and method for producing nonaqueous electrolyte power storage element | |
| WO2022249667A1 (en) | Nonaqueous electrolyte power storage element and power storage device | |
| WO2021100858A1 (en) | Electricity storage element and electricity storage device | |
| JP2022007093A (en) | Nonaqueous electrolyte power storage device | |
| JP2023117881A (en) | Non-aqueous electrolyte storage element | |
| JP2023056402A (en) | Nonaqueous electrolyte power storage element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230208 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230919 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20231114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240115 |