JP2006156268A - Nonaqueous electrolyte solution secondary battery and nonaqueous electrolyte solution secondary battery pack - Google Patents
Nonaqueous electrolyte solution secondary battery and nonaqueous electrolyte solution secondary battery pack Download PDFInfo
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- JP2006156268A JP2006156268A JP2004348090A JP2004348090A JP2006156268A JP 2006156268 A JP2006156268 A JP 2006156268A JP 2004348090 A JP2004348090 A JP 2004348090A JP 2004348090 A JP2004348090 A JP 2004348090A JP 2006156268 A JP2006156268 A JP 2006156268A
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- Prior art keywords
- secondary battery
- carbonate
- electrolyte secondary
- aqueous electrolyte
- battery
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 76
- 230000007246 mechanism Effects 0.000 claims abstract description 36
- -1 cyclic carboxylate Chemical class 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 24
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 22
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 20
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 19
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 17
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 17
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 15
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001555 benzenes Chemical class 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 6
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 150000001923 cyclic compounds Chemical group 0.000 claims description 4
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 claims description 3
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims description 3
- ALZLTHLQMAFAPA-UHFFFAOYSA-N 3-Methylbutyrolactone Chemical compound CC1COC(=O)C1 ALZLTHLQMAFAPA-UHFFFAOYSA-N 0.000 claims description 3
- ALWUKGXLBSQSMA-UHFFFAOYSA-N 5-Hexyldihydro-5-methyl-2(3H)-furanone Chemical compound CCCCCCC1(C)CCC(=O)O1 ALWUKGXLBSQSMA-UHFFFAOYSA-N 0.000 claims description 3
- HBJICDATLIMQTJ-UHFFFAOYSA-N C(O)(O)=O.C(=C)C=CC=C Chemical compound C(O)(O)=O.C(=C)C=CC=C HBJICDATLIMQTJ-UHFFFAOYSA-N 0.000 claims description 3
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 claims description 3
- VJRTZEWWUALMFH-UHFFFAOYSA-N carbonic acid;pent-1-yne Chemical compound OC(O)=O.CCCC#C VJRTZEWWUALMFH-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 3
- OALYTRUKMRCXNH-QMMMGPOBSA-N gamma-nonanolactone Chemical compound CCCCC[C@H]1CCC(=O)O1 OALYTRUKMRCXNH-QMMMGPOBSA-N 0.000 claims description 3
- IPBFYZQJXZJBFQ-UHFFFAOYSA-N gamma-octalactone Chemical compound CCCCC1CCC(=O)O1 IPBFYZQJXZJBFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007257 malfunction Effects 0.000 abstract description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 description 27
- 238000007600 charging Methods 0.000 description 25
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 17
- 239000007774 positive electrode material Substances 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000002159 abnormal effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QOTQFLOTGBBMEX-UHFFFAOYSA-N alpha-angelica lactone Chemical compound CC1=CCC(=O)O1 QOTQFLOTGBBMEX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
本発明は、非水電解液二次電池及び非水電解液二次電池パックに関する。 The present invention relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery pack.
近年、パソコンおよび携帯電話等の電子機器の小型軽量化、コードレス化が急速に進んでおり、これらの駆動用電源として高エネルギー密度を有する二次電池が要求されている。中でもリチウムを活物質とする非水電解液二次電池は、高電圧、高エネルギー密度を有する電池として期待が大きい。 In recent years, electronic devices such as personal computers and mobile phones are rapidly becoming smaller and lighter, and cordless, and secondary batteries having high energy density are required as power sources for driving these devices. Among them, a nonaqueous electrolyte secondary battery using lithium as an active material is highly expected as a battery having a high voltage and a high energy density.
リチウムイオン二次電池の正極活物質には、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎＯ2、ＬｉＭｎ2Ｏ4などのリチウム含有複合酸化物が用いられている。これらの正極活物質は、充放電を行うことにより膨張・収縮を繰り返す。この際に結晶構造の破壊や粒子の割れ等が発生するため、充放電サイクルに伴う容量低下や内部抵抗の増加を生じる。このような問題に対し、コバルトまたはニッケルの一部を他の元素で置換することにより、結晶構造の安定化を図るという報告がある。例えば、正極活物質のコバルトの一部をマグネシウムなどの元素と置換することにより、サイクル特性や安全性を向上させるという報告がある（例えば、特許文献１〜３参照）。
しかし、上記のような従来の技術では、充放電サイクル特性の劣化を抑制することができる反面、例えば、充電状態の電池を高温状態で保存した場合には、電池内におけるガス発生量が比較的多くなることが確認されている。特に、電池内部に電池の内圧上昇により作動する電流遮断機構を有する電池の場合、高温保存時のガス発生による誤作動が生じることがある。ガス発生量が増加する原因は現在のところ確かではないが、コバルトの一部をマグネシウムで置換した正極活物質は、電子伝導性が高く、活物質表面が活性なため、非水電解液との反応性が高まり、非水電解液の分解が促進されるためと考えられている。 However, in the conventional technology as described above, deterioration of charge / discharge cycle characteristics can be suppressed, but when a charged battery is stored at a high temperature, for example, the amount of gas generated in the battery is relatively low. It has been confirmed that it will increase. In particular, in the case of a battery having a current interruption mechanism that operates due to an increase in the internal pressure of the battery, a malfunction may occur due to gas generation during high temperature storage. The cause of the increased gas generation rate is not certain at present, but the positive electrode active material in which a part of cobalt is replaced with magnesium has high electron conductivity and the active material surface is active. It is considered that the reactivity is increased and the decomposition of the non-aqueous electrolyte is promoted.
本発明は、正極、負極、非水電解液および電池内部に電池の内圧上昇により作動する電流遮断機構を備えてなる非水電解液二次電池であって、前記正極が一般式：Ｌｉa（Ｃｏ1-x-yＭｇxＭy）bＯc（Ｍは、Ｍｎ、Ｎｉ、Ｙ、Ｙｂ、Ｃａ、Ａｌ、Ｔｉ、Ｃｕ、Ｚｎ、ＳｒおよびＢａからなる群より選択される少なくとも一種、０≦ａ≦１．０５、０．００５≦ｘ≦０．１５、０≦ｙ≦０．２５、０．８５≦ｂ≦１．１、１．８≦ｃ≦２．１）で表されるリチウム含有遷移金属酸化物、前記負極が炭素材料、前記非水電解液が、（Ａ）環状カルボン酸エステルを含有する非水溶媒ならびに前記非水溶媒に溶解させた溶質からなる非水電解液二次電池に関する。 The present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, and a current interruption mechanism that operates when the internal pressure of the battery increases, and the positive electrode is represented by the general formula: Li a ( at least one Co 1-xy Mg x M y ) b O c (M is, Mn, Ni, Y, Yb , Ca, Al, Ti, Cu, Zn, is selected from the group consisting of Sr and Ba, 0 ≦ a ≦ 1.05, 0.005 ≦ x ≦ 0.15, 0 ≦ y ≦ 0.25, 0.85 ≦ b ≦ 1.1, 1.8 ≦ c ≦ 2.1) The present invention relates to a non-aqueous electrolyte secondary battery comprising a metal oxide, the negative electrode is a carbon material, and the non-aqueous electrolyte is composed of (A) a non-aqueous solvent containing a cyclic carboxylic acid ester and a solute dissolved in the non-aqueous solvent. .
さらに、前記非水溶媒は、（Ａ）環状カルボン酸エステル、（Ｂ）炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステルおよび（Ｃ）炭素−炭素不飽和結合を有しない環状炭酸エステルを含有する非水溶媒ならびに前記非水溶媒に溶解させた溶質からなることがより好ましい。 Further, the non-aqueous solvent comprises (A) a cyclic carboxylic acid ester, (B) a cyclic carbonate having at least one carbon-carbon unsaturated bond, and (C) a cyclic carbonate having no carbon-carbon unsaturated bond. More preferably, it comprises a nonaqueous solvent contained and a solute dissolved in the nonaqueous solvent.
前記環状カルボン酸エステル（Ａ）が、γ−ブチロラクトン（ＧＢＬ）、γ−バレロラクトン（ＧＶＬ）、α−アセチル−γ−ブチロラクトン、α−メチル−γ−ブチロラクトン、β−メチル−γ−ブチロラクトン、α−アンゲリカラクトン、α−メチレン−γ−ブチロラクトン、γ−ヘキサノラクトン、γ−ノナノラクトン、γ−オクタノラクトン、γ−メチル−γ−デカノラクトンからなる群より選択される少なくとも一種であり、前記炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステル（Ｂ）が、ビニレンカーボネート（ＶＣ）を始めとして、３−メチルビニレンカーボネート、３，４−ジメチルビニレンカーボネート、３−エチルビニレンカーボネート、３，４−ジエチルビニレンカーボネート、３−プロピルビニレンカーボネート、３，４−ジプロピルビニレンカーボネート、３−フェニルビニレンカーボネート、３，４−ジフェニルビニレンカーボネート、ビニルエチレンカーボネート（ＶＥＣ）、ジビニルエチレンカーボネート（ＤＶＥＣ）からなる群より選択される少なくとも一種であり、前記炭素−炭素不飽和結合を有しない環状炭酸エステル（Ｃ）が、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ブチレンカーボネート（ＢＣ）からなる群より選択される少なくとも一種であることが好ましい。 The cyclic carboxylic acid ester (A) is γ-butyrolactone (GBL), γ-valerolactone (GVL), α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, α -Angelica lactone, α-methylene-γ-butyrolactone, γ-hexanolactone, γ-nonanolactone, γ-octanolactone, γ-methyl-γ-decanolactone, at least one selected from the group consisting of carbon- Cyclic carbonates (B) having at least one carbon unsaturated bond are vinylene carbonate (VC), 3-methyl vinylene carbonate, 3,4-dimethyl vinylene carbonate, 3-ethyl vinylene carbonate, 3,4- Diethyl vinylene carbonate, 3-propyl vinylene carbonate , 3,4-dipropyl vinylene carbonate, 3-phenyl vinylene carbonate, 3,4-diphenyl vinylene carbonate, vinyl ethylene carbonate (VEC), and divinyl ethylene carbonate (DVEC). The cyclic carbonate (C) having no carbon-carbon unsaturated bond is preferably at least one selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), and butylene carbonate (BC).
前記非水溶媒が、さらに鎖状炭酸エステル（Ｄ）を含有することが好ましく、鎖状炭酸エステル（Ｄ）は、ジメチルカーボネート、エチルメチルカーボネートおよびジエチルカーボネートからなる群より選択される少なくとも一種であることがより好ましい。前記溶質は、ＬｉＰＦ6とＬｉＢＦ4との混合物であることが好ましい。さらに前記非水溶媒が、フェニル基および前記フェニル基に隣接する環状化合物基からなるベンゼン誘導体を含有することが好ましい。本発明によれば、電流遮断機構を備えた高い安全性を有する非水電解液二次電池において、充放電サイクルに伴う容量低下を抑制するとともに、高温保存時に電流遮断機構の誤作動のない非水電解液二次電池を提供することができる。 The non-aqueous solvent preferably further contains a chain carbonate ester (D), and the chain carbonate ester (D) is at least one selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. It is more preferable. The solute is preferably a mixture of LiPF 6 and LiBF 4 . Furthermore, it is preferable that the non-aqueous solvent contains a benzene derivative composed of a phenyl group and a cyclic compound group adjacent to the phenyl group. According to the present invention, in a highly safe non-aqueous electrolyte secondary battery equipped with a current interruption mechanism, it is possible to suppress a decrease in capacity associated with a charge / discharge cycle and to prevent malfunction of the current interruption mechanism during high temperature storage. A water electrolyte secondary battery can be provided.
また、本発明の非水電解液二次電池は電流遮断機構に併せて、感熱性の保護素子を取り付けることにより、異常充電時の安全性をより高めることができる。感熱性の保護素子としては、ＰＴＣ、温度ヒューズ、サーミスタ、サーモスタットを上げることができ、これらを単独で用いてもよく、組み合わせて用いても良い。 In addition, the nonaqueous electrolyte secondary battery of the present invention can be further improved in safety during abnormal charging by attaching a heat-sensitive protective element in addition to the current interruption mechanism. PTC, thermal fuse, thermistor, and thermostat can be raised as the heat-sensitive protective element, and these may be used alone or in combination.
さらに、本発明の非水電解液二次電池を単数または複数使用した電池パックに、感熱性の保護素子として、ＰＴＣ、温度ヒューズ、サーミスタ、サーモスタットを単独や、組み合わせて取り付けることにより異常充電時の安全性を向上させることができる。 Furthermore, a battery pack using one or a plurality of the non-aqueous electrolyte secondary batteries of the present invention can be used as a heat-sensitive protective element by attaching a PTC, a thermal fuse, a thermistor, or a thermostat, alone or in combination, during abnormal charging. Safety can be improved.
以上のように、本発明では、正極、負極、非水電解液および電池内部に電池の内圧上昇により作動する電流遮断機構を備えてなる非水電解液二次電池において、前記正極が一般式：Ｌｉa（Ｃｏ1-x-yＭｇxＭy）bＯc（Ｍは、Ｍｎ、Ｎｉ、Ｙ、Ｙｂ、Ｃａ、Ａｌ、Ｔｉ、Ｃｕ、Ｚｎ、ＳｒおよびＢａからなる群より選択される少なくとも一種、０≦ａ≦１．０５、０．００５≦ｘ≦０．１５、０≦ｙ≦０．２５、０．８５≦ｂ≦１．１、１．８≦ｃ≦２．１）で表されるリチウム含有遷移金属酸化物からなり、前記負極が炭素材料からなり、前記非水電解液が、（Ａ）環状カルボン酸エステルを含有する非水溶媒ならびに前記非水溶媒に溶解させた溶質からなることにより、充放電サイクル特性に優れ、且つ電池を高温条件下に一定時間放置しても電流遮断機構が誤作動を起こさない非水電解液二次電池を提供することができる。 As described above, in the present invention, in the non-aqueous electrolyte secondary battery including the positive electrode, the negative electrode, the non-aqueous electrolyte, and the current interruption mechanism that operates by increasing the internal pressure of the battery, the positive electrode has the general formula: at least one li a (Co 1-xy Mg x M y) b O c (M is, for Mn, Ni, Y, Yb, Ca, Al, Ti, Cu, Zn, is selected from the group consisting of Sr and Ba, 0 ≦ a ≦ 1.05, 0.005 ≦ x ≦ 0.15, 0 ≦ y ≦ 0.25, 0.85 ≦ b ≦ 1.1, 1.8 ≦ c ≦ 2.1) It consists of a lithium-containing transition metal oxide, the negative electrode is made of a carbon material, and the non-aqueous electrolyte is composed of (A) a non-aqueous solvent containing a cyclic carboxylic acid ester and a solute dissolved in the non-aqueous solvent. Therefore, it has excellent charge / discharge cycle characteristics and the battery is released under high temperature conditions for a certain period of time. It is possible to provide a nonaqueous electrolyte secondary battery which does not cause the operating current cut-off mechanism false be.
そして、電流遮断機構に併せて、感熱性の保護素子を取り付けることにより、異常充電時の安全性をより高めた非水電解液二次電池を提供することができる。 And the nonaqueous electrolyte secondary battery which improved safety | security at the time of abnormal charge more can be provided by attaching a heat-sensitive protective element in addition to the electric current interruption mechanism.
さらに、本発明の非水電解液二次電池を単数または複数使用した電池パックに、感熱性の保護素子を取り付けることにより異常充電時の安全性をより高めた非水電解液二次電池パックを提供することができる。 Furthermore, a non-aqueous electrolyte secondary battery pack that further improves safety during abnormal charging by attaching a heat-sensitive protective element to a battery pack that uses one or more non-aqueous electrolyte secondary batteries of the present invention. Can be provided.
本発明では、一般式：Ｌｉa（Ｃｏ1-x-yＭｇxＭy）bＯc（Ｍは、Ｍｎ、Ｎｉ、Ｙ、Ｙｂ、Ｃａ、Ａｌ、Ｔｉ、Ｃｕ、Ｚｎ、ＳｒおよびＢａからなる群より選択される少なくとも一種、０≦ａ≦１．０５、０．００５≦ｘ≦０．１５、０≦ｙ≦０．２５、０．８５≦ｂ≦１．１、１．８≦ｃ≦２．１）で表されるリチウム含有複合酸化物からなる正極活物質を用いる。前記複合酸化物の結晶においては、マグネシウムでコバルトの一部が置換されているため、結晶構造が安定であり、充放電サイクルに伴う結晶構造の破壊や粒子の割れが発生しにくい。従って、電池の容量低下が抑制され、サイクル寿命が向上する。 In the present invention, the general formula: Li a (Co 1-xy Mg x M y) b O c (M is, Mn, Ni, Y, Yb , Ca, Al, Ti, Cu, Zn, the group consisting of Sr and Ba At least one selected from 0 ≦ a ≦ 1.05, 0.005 ≦ x ≦ 0.15, 0 ≦ y ≦ 0.25, 0.85 ≦ b ≦ 1.1, 1.8 ≦ c ≦ 2. The positive electrode active material which consists of lithium containing complex oxide represented by .1) is used. In the complex oxide crystal, magnesium is partially substituted with magnesium, so that the crystal structure is stable, and the crystal structure is not easily broken or the particles are cracked due to the charge / discharge cycle. Therefore, the capacity reduction of the battery is suppressed and the cycle life is improved.
マグネシウムの含有率ｘが０．００５未満の場合、複合酸化物の結晶構造の安定化が不十分となる。従って、充放電を繰り返すと、内部抵抗が増大し、サイクル特性が大きく劣化する。一方、含有率ｘが０．１５をこえると、正極活物質の充放電容量が低下する。このことから、Ｍｇの含有率ｘは、０．００５≦ｘ≦０．１５を満たす必要がある。 When the magnesium content x is less than 0.005, stabilization of the crystal structure of the composite oxide becomes insufficient. Therefore, when charging / discharging is repeated, the internal resistance increases and the cycle characteristics are greatly degraded. On the other hand, when the content rate x exceeds 0.15, the charge / discharge capacity of the positive electrode active material decreases. Therefore, the Mg content x needs to satisfy 0.005 ≦ x ≦ 0.15.
また、前記複合酸化物は、元素Ｍを含むことにより耐熱性の向上やサイクル特性のさらなる改善が実現できる。ただし、元素Ｍの含有率ｙが、０．２５より大きくなると、高温保存時のガス発生量が増加したり、活物質の充放電容量が低下したりする。このことから、Ｍの含有率ｙは、０≦ｙ≦０．２５を満たす必要がある。 Moreover, the complex oxide can realize improvement in heat resistance and further improvement in cycle characteristics by including the element M. However, when the content rate y of the element M becomes larger than 0.25, the amount of gas generated during high-temperature storage increases or the charge / discharge capacity of the active material decreases. Therefore, the M content y needs to satisfy 0 ≦ y ≦ 0.25.
ａが１．０５を超えると、Ｌｉ２ＯやＬｉ２ＣＯ３などが生成し、これが分解して、Ｏ２やＣＯ２などのガスが発生する。 When a exceeds 1.05, Li 2 O, Li 2 CO 3 and the like are generated and decomposed to generate gases such as O 2 and CO 2 .
ｂが０．８５未満では、結晶構造の安定化が不十分となり、サイクル特性が低下する。逆に、ｂが１．１を超えると、ＣｏＣＯ３が生成し、ＣＯ２などのガスが発生する。 When b is less than 0.85, the crystal structure is not sufficiently stabilized and the cycle characteristics are deteriorated. On the contrary, when b exceeds 1.1, CoCO 3 is generated and gas such as CO 2 is generated.
ｃが１．８未満では、酸素欠損型の結晶構造になり、結晶構造の安定化が不十分となり、サイクル特性が低下する。逆に、ｃが２．１を超えるとＯ２ガスが発生する。 When c is less than 1.8, an oxygen deficient crystal structure is obtained, the crystal structure is not sufficiently stabilized, and the cycle characteristics are deteriorated. Conversely, when c exceeds 2.1, O 2 gas is generated.
本発明の非水電解液二次電池は、電池内のガス圧力が所定値以上になると作動する電流遮断機構を備えることにより、異常充電時の安全性を大幅に向上させることができる。 The non-aqueous electrolyte secondary battery of the present invention can significantly improve safety during abnormal charging by providing a current interrupt mechanism that operates when the gas pressure in the battery reaches a predetermined value or higher.
電流遮断機構は、電池が異常充電されると電池内で電解液が分解してガスが発生し、電池内の圧力が上昇することにより充電電流を遮断する機構である。 The current interruption mechanism is a mechanism that interrupts the charging current when the battery is abnormally charged and the electrolyte is decomposed in the battery to generate gas and the pressure in the battery rises.
電流遮断機構としては、電池内の圧力上昇で変形することにより充電電流接点が切れる機構、センサーで電池内の圧力を検知することにより充電を停止する外部回路、センサーで電池の変形を検知することにより充電を停止する外部回路などがあげられるが、電池内の圧力上昇で変形することにより充電電流接点が切れる機構が、最もシンプルで効果が高いので好ましい。 Current cut-off mechanism includes a mechanism that breaks the charging current contact by deformation due to pressure rise in the battery, an external circuit that stops charging by detecting the pressure in the battery with a sensor, and detection of battery deformation with a sensor Although an external circuit for stopping charging is given by the above, a mechanism in which the charging current contact is cut by deformation due to an increase in pressure in the battery is preferable because it is the simplest and most effective.
本発明の非水電解液二次電池には、（Ａ）環状カルボン酸エステルを含有する非水溶媒に溶質を溶解させた非水電解液を用いることにより、前記正極を用いた電流遮断機構を備える非水電解液二次電池が高温状態に一定時間保存された場合の電池内におけるガス発生を大幅に減少させ、高温保存時に電流遮断機構が誤作動しない非水電解液二次電池を提供することが可能となる。 The non-aqueous electrolyte secondary battery of the present invention has a current blocking mechanism using the positive electrode by using a non-aqueous electrolyte solution in which a solute is dissolved in a non-aqueous solvent containing (A) a cyclic carboxylic acid ester. Provided is a non-aqueous electrolyte secondary battery that significantly reduces gas generation in the battery when the non-aqueous electrolyte secondary battery is stored in a high temperature state for a certain period of time and does not cause a malfunction of the current interruption mechanism during high temperature storage. It becomes possible.
上記非水電解液を用いることで高温保存時のガス発生を大幅に減少させ、電流遮断機構の誤作動を防止することができる理由を以下に示す。前述のようにコバルトの一部をマグネシウムで置換した正極活物質は、電子伝導性が高く、活物質表面が活性なため、電池を高温保存した場合に、非水電解液との反応性が高まり、非水電解液の分解が促進されてガス発生が多くなると考えられている。 The reason why the generation of gas during high-temperature storage can be greatly reduced by using the non-aqueous electrolyte and malfunction of the current interrupting mechanism can be prevented will be described below. As described above, the positive electrode active material in which a part of cobalt is substituted with magnesium has high electron conductivity and the active material surface is active, so that the reactivity with the non-aqueous electrolyte increases when the battery is stored at high temperature. It is considered that the decomposition of the non-aqueous electrolyte is promoted to increase gas generation.
環状カルボン酸エステル（Ａ）を含有する非水電解液を用いた場合、環状カルボン酸エステルが正極表面で分解して分解生成物が正極表面に緻密な被膜を形成し、電解液と正極との直接の接触を抑制する結果、高温保存時のガス発生を大幅に抑制することができる。また、環状カルボン酸エステル（Ａ）は一部が負極表面で分解されるため、それを抑制するために炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステル（Ｂ）を併せて非水電解液に含有させることがより好ましい。炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステル（Ｂ）は、不飽和結合部が非常に重合しやすいため、負極上で連鎖的に重合反応を起こし、迅速に負極上に緻密で強固な被膜を形成する。この負極上に形成された被膜がリチウムイオン周囲の溶媒分子の負極への接触を阻止する物理的バリアーとなる結果、負極での環状カルボン酸エステルの還元分解が抑制される。 When the non-aqueous electrolyte containing the cyclic carboxylic acid ester (A) is used, the cyclic carboxylic acid ester decomposes on the surface of the positive electrode, and the decomposition product forms a dense film on the surface of the positive electrode. As a result of suppressing direct contact, gas generation during high temperature storage can be significantly suppressed. Moreover, since a part of cyclic carboxylic acid ester (A) is decomposed | disassembled on the negative electrode surface, in order to suppress it, non-aqueous electrolysis is combined with cyclic carbonate (B) which has at least one carbon-carbon unsaturated bond. More preferably, it is contained in the liquid. In the cyclic carbonate (B) having at least one carbon-carbon unsaturated bond, since the unsaturated bond portion is very easily polymerized, a chain polymerization reaction occurs on the negative electrode, and the dense and strong on the negative electrode quickly. A smooth coating is formed. As a result of the coating formed on the negative electrode becoming a physical barrier that prevents contact of solvent molecules around lithium ions with the negative electrode, reductive decomposition of the cyclic carboxylic acid ester at the negative electrode is suppressed.
さらに、環状カルボン酸エステル（Ａ）に炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステル（Ｂ）を含有させた電解液を用いて作製した電池を高温条件下に一定時間放置した場合、前述のように熱により負極上での環状炭酸エステル（Ｂ）の分解が促進されて負極上に過剰の被膜が形成される。その結果、負極へのリチウムイオンの挿入、脱離がスムーズに行われなくなり、電池の充放電特性が低下する傾向にある。 Furthermore, when a battery prepared using an electrolytic solution in which the cyclic carbonate (A) contains a cyclic carbonate (B) having at least one carbon-carbon unsaturated bond is left under a high temperature condition for a certain period of time, As described above, the decomposition of the cyclic carbonate (B) on the negative electrode is accelerated by heat, and an excessive film is formed on the negative electrode. As a result, lithium ions are not smoothly inserted and removed from the negative electrode, and the charge / discharge characteristics of the battery tend to deteriorate.
そこで、さらに不飽和結合を有しない環状炭酸エステル（Ｃ）を電解液に含有させることにより、高温条件下での環状炭酸エステル（Ｂ）の過剰の重合反応を抑制することができるため、より好ましい。エチレンカーボネートやプロピレンカーボネート等の炭素−炭素不飽和結合を有しない環状炭酸エステル（Ｃ）も、ビニレンカーボネート等の炭素−炭素不飽和結合を有する環状炭酸エステル（Ｂ）と同様に負極上で還元分解されて分解生成物による被膜を形成する。ただし、エチレンカーボネートやプロピレンカーボネートは、炭素−炭素不飽和結合を有しないため、不飽和結合の重合反応で被膜を形成するビニレンカーボネート等に比べて被膜の形成が非常に遅い。 Therefore, it is more preferable that the cyclic carbonate (C) having no unsaturated bond is further contained in the electrolytic solution because excessive polymerization reaction of the cyclic carbonate (B) under high temperature conditions can be suppressed. . Cyclic carbonates (C) having no carbon-carbon unsaturated bonds such as ethylene carbonate and propylene carbonate are reduced and decomposed on the negative electrode in the same manner as cyclic carbonates (B) having carbon-carbon unsaturated bonds such as vinylene carbonate. As a result, a film is formed from the decomposition products. However, since ethylene carbonate and propylene carbonate do not have a carbon-carbon unsaturated bond, the formation of a film is very slow compared to vinylene carbonate or the like that forms a film by an unsaturated bond polymerization reaction.
ビニレンカーボネートの連鎖的な重合反応の途中において、エチレンカーボネートやプロピレンカーボネートが重合中間体に結合した場合、その部位の反応が非常に遅くなり、高温条件下でのビニレンカーボネートの過剰な重合反応が抑制される。その結果、高温条件下に一定時間放置した後も良好な充放電特性を有する電池が実現できる。 When ethylene carbonate or propylene carbonate is bonded to the polymerization intermediate during the chain polymerization reaction of vinylene carbonate, the reaction at that site becomes very slow, and excessive polymerization reaction of vinylene carbonate under high temperature conditions is suppressed. Is done. As a result, a battery having good charge / discharge characteristics can be realized even after being left for a certain period of time under high temperature conditions.
環状カルボン酸エステル（Ａ）としては、γ−ブチロラクトン（ＧＢＬ）、γ−バレロラクトン（ＧＶＬ）、α−アセチル−γ−ブチロラクトン、α−メチル−γ−ブチロラクトン、β−メチル−γ−ブチロラクトン、α−アンゲリカラクトン、α−メチレン−γ−ブチロラクトン、γ−ヘキサノラクトン、γ−ノナノラクトン、γ−オクタノラクトン、γ−メチル−γ−デカノラクトン等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the cyclic carboxylic acid ester (A) include γ-butyrolactone (GBL), γ-valerolactone (GVL), α-acetyl-γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, α -Angelica lactone, α-methylene-γ-butyrolactone, γ-hexanolactone, γ-nonanolactone, γ-octanolactone, γ-methyl-γ-decanolactone and the like. These may be used alone or in combination of two or more.
炭素−炭素不飽和結合を少なくとも１つ有する環状炭酸エステル（Ｂ）としては、ビニレンカーボネート（ＶＣ）を始めとして、３−メチルビニレンカーボネート、３，４−ジメチルビニレンカーボネート、３−エチルビニレンカーボネート、３，４−ジエチルビニレンカーボネート、３−プロピルビニレンカーボネート、３，４−ジプロピルビニレンカーボネート、３−フェニルビニレンカーボネート、３，４−ジフェニルビニレンカーボネート、ビニルエチレンカーボネート（ＶＥＣ）、ジビニルエチレンカーボネート（ＤＶＥＣ）等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの化合物は、その水素原子の一部がフッ素原子で置換されていてもよい。特に、ビニレンカーボネートとビニルエチレンカーボネートとを併用すると、ビニルエチレンカーボネートが高温におけるビニレンカーボネートの反応活性を抑制するため、電池の高温保存特性が向上する点で好ましい。 Examples of the cyclic carbonate (B) having at least one carbon-carbon unsaturated bond include vinylene carbonate (VC), 3-methyl vinylene carbonate, 3,4-dimethyl vinylene carbonate, 3-ethyl vinylene carbonate, 3 , 4-diethyl vinylene carbonate, 3-propyl vinylene carbonate, 3,4-dipropyl vinylene carbonate, 3-phenyl vinylene carbonate, 3,4-diphenyl vinylene carbonate, vinyl ethylene carbonate (VEC), divinyl ethylene carbonate (DVEC), etc. Is mentioned. These may be used alone or in combination of two or more. In these compounds, part of the hydrogen atoms may be substituted with fluorine atoms. In particular, when vinylene carbonate and vinyl ethylene carbonate are used in combination, vinyl ethylene carbonate suppresses the reaction activity of vinylene carbonate at high temperatures, which is preferable in terms of improving the high-temperature storage characteristics of the battery.
炭素−炭素不飽和結合を有しない環状炭酸エステル（Ｃ）としては、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、ブチレンカーボネート（ＢＣ）等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの化合物は、その水素原子の一部がフッ素原子で置換されていてもよい。 Examples of the cyclic carbonate (C) having no carbon-carbon unsaturated bond include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC) and the like. These may be used alone or in combination of two or more. In these compounds, part of the hydrogen atoms may be substituted with fluorine atoms.
前記非水溶媒における環状カルボン酸エステル（Ａ）の含有量は、１０体積％〜９７体積％であることが好ましい。前記非水溶媒における炭素−炭素不飽和結合を少なくとも一つ有する環状炭酸エステル（Ｂ）の含有量は、０．５体積％〜２０体積％であることが好ましい。前記非水溶媒における炭素−炭素不飽和結合を有しない環状炭酸エステル（Ｃ）の含有量は、４０体積％以下であることが好ましく、０．１体積％〜３０体積％がさらに好ましく、０．１体積％〜２０体積％が最も好ましい。 The content of the cyclic carboxylic acid ester (A) in the non-aqueous solvent is preferably 10% by volume to 97% by volume. The content of the cyclic carbonate (B) having at least one carbon-carbon unsaturated bond in the non-aqueous solvent is preferably 0.5% by volume to 20% by volume. The content of the cyclic carbonate (C) having no carbon-carbon unsaturated bond in the non-aqueous solvent is preferably 40% by volume or less, more preferably 0.1% by volume to 30% by volume, and 1% by volume to 20% by volume is most preferable.
前記非水溶媒は、さらに、鎖状炭酸エステル（Ｄ）を含有することができる。非水溶媒が鎖状炭酸エステル（Ｄ）を含有する場合、非水溶媒の粘度が低下し、低温時の電池の充放電特性をさらに向上させることができる。鎖状炭酸エステル（Ｄ）としては、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）、ジエチルカーボネート（ＤＥＣ）等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記非水溶媒における鎖状炭酸エステルの含有量は、５０体積％以下であることが好ましく、０．１体積％〜３０体積％がさらに好ましく、０．１体積％〜２０体積％が最も好ましい。 The non-aqueous solvent can further contain a chain carbonate ester (D). When the non-aqueous solvent contains the chain carbonate ester (D), the viscosity of the non-aqueous solvent decreases, and the charge / discharge characteristics of the battery at low temperatures can be further improved. Examples of the chain carbonate ester (D) include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC). These may be used alone or in combination of two or more. The content of the chain carbonate in the non-aqueous solvent is preferably 50% by volume or less, more preferably 0.1% by volume to 30% by volume, and most preferably 0.1% by volume to 20% by volume.
また、過充電時に分解して電極上に被膜を形成し、電池を不活性化する従来からよく知られているベンゼン誘導体（Ｆ）を本発明にかかる非水溶媒に添加することも効果的である。ベンゼン誘導体（Ｆ）には、フェニル基および前記フェニル基に隣接する環状化合物基からなるベンゼン誘導体を用いることが好ましい。 It is also effective to add a well-known benzene derivative (F), which decomposes during overcharge to form a film on the electrode and inactivates the battery, to the non-aqueous solvent according to the present invention. is there. As the benzene derivative (F), a benzene derivative comprising a phenyl group and a cyclic compound group adjacent to the phenyl group is preferably used.
前記環状化合物基としては、フェニル基、環状エーテル基、環状エステル基、シクロアルキル基、フェノキシ基などが好ましい。ベンゼン誘導体（Ｆ）の具体例としては、シクロヘキシルベンゼン、ビフェニル、ジフェニルエーテルなどが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。前記非水溶媒におけるベンゼン誘導体（Ｆ）の含有量は、１０体積％以下であることが好ましい。 As the cyclic compound group, a phenyl group, a cyclic ether group, a cyclic ester group, a cycloalkyl group, a phenoxy group, and the like are preferable. Specific examples of the benzene derivative (F) include cyclohexylbenzene, biphenyl, diphenyl ether and the like. These may be used alone or in combination of two or more. The content of the benzene derivative (F) in the non-aqueous solvent is preferably 10% by volume or less.
前記非水溶媒に溶解させる溶質は、本発明では特に限定されず、非水電解液二次電池で通常用いられているいずれの溶質でも使用できる。具体的には、ＬｉＣｌＯ4、ＬｉＡｓＦ6、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ（ＣＦ3ＳＯ2）（Ｃ4Ｆ9ＳＯ2）、ＬｉＢ［Ｃ6Ｆ3（ＣＦ3）2−３，５］4、ＬｉＰＦa（ＣbＦ2b+1）6-a（ａは１から５の整数、ｂは１以上の整数である）、ＬｉＰＦc（ＣdＦ2d+1ＳＯ2）6-c（ｃは１から５の整数、ｄは１以上の整数である）、ＬｉＢＦe（ＣfＦ2f+1）4-e（ｅは１から３の整数、ｆは１以上の整数である）、ＬｉＢＦg（ＣhＦ2h+1ＳＯ2）4-g（ｇは１から３の整数、ｈは１以上の整数である）等が使用できる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。中でも、ＬｉＰＦ6とＬｉＢＦ4とを併用することが特に好ましい。ＬｉＰＦ6は、電気特性に優れる一方で、フッ酸を生成するため化学的に不安定である。特に、本発明にかかる電解液の成分である環状カルボン酸エステル（Ａ）は、フッ酸により分解しやすいため、例えば電池のサイクル特性が阻害されるおそれがある。一方、ＬｉＢＦ4のみを使用した場合には、ＬｉＢＦ4の解離度が低い、あるいは負極に黒鉛を用いる場合に表面に形成される保護被膜が弱くなるなどの理由により、やはり電池のサイクル特性が阻害される。それに対し、ＬｉＢＦ4をＬｉＰＦ6と併用すると、電池のサイクル特性が向上する。このＬｉＢＦ4の添加効果は少量でも得ることができる。ＬｉＰＦ6の量は全溶質量の２モル％以上であることが好ましい。一方、ＬｉＢＦ4の量は、全溶質量の１０モル％以上であることが好ましい。前記非水電解液における溶質濃度は、０．８モル／リットル〜２．５モル／リットルが好ましい。 The solute dissolved in the non-aqueous solvent is not particularly limited in the present invention, and any solute normally used in non-aqueous electrolyte secondary batteries can be used. Specifically, LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) ( C 4 F 9 SO 2), LiB [C 6 F 3 (CF 3) 2 -3,5] 4, LiPF a (C b F 2b + 1) 6-a (a is from 1 5 integers, b is LiPF c (C d F 2d + 1 SO 2 ) 6-c (c is an integer of 1 to 5, d is an integer of 1 or more), LiBF e (C f F 2f + 1 ) 4-e (e is an integer of 1 to 3, f is an integer of 1 or more), LiBF g (C h F 2h + 1 SO 2 ) 4-g (g is an integer of 1 to 3, h is Or an integer greater than or equal to 1). These may be used alone or in combination of two or more. Among these, it is particularly preferable to use LiPF 6 and LiBF 4 in combination. LiPF 6 is chemically unstable because it produces hydrofluoric acid while it has excellent electrical properties. In particular, the cyclic carboxylic acid ester (A), which is a component of the electrolytic solution according to the present invention, is easily decomposed by hydrofluoric acid, and thus, for example, the cycle characteristics of the battery may be hindered. On the other hand, when only LiBF 4 is used, the cycle characteristics of the battery are also hindered because the degree of dissociation of LiBF 4 is low or the protective film formed on the surface becomes weak when graphite is used for the negative electrode. Is done. On the other hand, when LiBF 4 is used in combination with LiPF 6 , the cycle characteristics of the battery are improved. The effect of adding LiBF 4 can be obtained even in a small amount. The amount of LiPF 6 is preferably 2 mol% or more of the total dissolved mass. On the other hand, the amount of LiBF 4 is preferably 10 mol% or more of the total dissolved mass. The solute concentration in the non-aqueous electrolyte is preferably 0.8 mol / liter to 2.5 mol / liter.
前記リチウム含有遷移金属酸化物Ｌｉa（Ｃｏ1-x-yＭｇxＭy）bＯcは、例えば、リチウム塩と、マグネシウム塩と、Ｍで表される金属の塩と、コバルト塩とを酸化雰囲気下で高温で焼成することにより、得ることができる。正極活物質を合成するための原料としては、以下のものを用いることができる。リチウム塩としては、炭酸リチウム、水酸化リチウム、硝酸リチウム、硫酸リチウム、酸化リチウム等を用いることができる。マグネシウム塩としては、酸化マグネシウム、塩基性炭酸マグネシウム、塩化マグネシウム、フッ化マグネシウム、硝酸マグネシウム、硫酸マグネシウム、酢酸マグネシウム、蓚酸マグネシウム、硫化マグネシウム、水酸化マグネシウムを用いることができる。 The lithium-containing transition metal oxide Li a (Co 1-xy Mg x M y) b O c , for example, a lithium salt, a magnesium salt, a salt of the metal represented by M, oxidizing a cobalt salt atmosphere It can be obtained by firing at a high temperature under. As raw materials for synthesizing the positive electrode active material, the following can be used. As the lithium salt, lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, lithium oxide, or the like can be used. As the magnesium salt, magnesium oxide, basic magnesium carbonate, magnesium chloride, magnesium fluoride, magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium oxalate, magnesium sulfide, and magnesium hydroxide can be used.
同様にＭで表される金属の塩も既存のものが適宜使用できる。コバルト塩としては、酸化コバルト、水酸化コバルト等を用いることができる。また、共沈法により、マグネシウムや金属Ｍを含有する水酸化コバルトを作製した後、その水酸化コバルトとリチウム塩とを混合し、焼成することによっても前記リチウム含有遷移金属酸化物を得ることができる。
負極材料としては、熱分解炭素類、コークス類（ピッチコークス、ニードルコークス、石油コークス等）、グラファイト類、ガラス状炭素類、有機高分子化合物焼成体（フェノール樹脂、フラン樹脂等を適当な温度で焼成し炭素化したもの）、炭素繊維、活性炭素等の炭素材料が挙げられ、（００２）面の面間隔が０．３４０ｎｍ以下であるようなグラファイトを用いる場合、電池のエネルギー密度が向上する。
Similarly, existing metal salts represented by M can be used as appropriate. As the cobalt salt, cobalt oxide, cobalt hydroxide or the like can be used. Moreover, after producing cobalt hydroxide containing magnesium and metal M by coprecipitation, the lithium-containing transition metal oxide can also be obtained by mixing and baking the cobalt hydroxide and lithium salt. it can.
As the negative electrode material, pyrolytic carbons, cokes (pitch coke, needle coke, petroleum coke, etc.), graphites, glassy carbons, organic polymer compound fired bodies (phenol resin, furan resin, etc.) at an appropriate temperature. When the graphite having a (002) plane spacing of 0.340 nm or less is used, the energy density of the battery is improved.
正極材料は、例えば結着剤および導電剤と混練され、極板に加工される。また、負極材料は、例えば結着剤と混練され、極板に加工される。前記結着剤および導電剤には、従来公知のものをいずれも使用可能である。本発明の電池の形状等には、円筒型、角型、コイン型、ボタン型、大型等があり、正極、負極の態様をそれに応じて変更すればよい。 The positive electrode material is kneaded with, for example, a binder and a conductive agent and processed into an electrode plate. The negative electrode material is kneaded with, for example, a binder and processed into an electrode plate. Any conventionally known binder and conductive agent can be used. The shape and the like of the battery of the present invention include a cylindrical shape, a square shape, a coin shape, a button shape, a large size, and the like, and the aspect of the positive electrode and the negative electrode may be changed accordingly.
また、本発明の非水電解液二次電池は電流遮断機構に併せて、感熱性の保護素子が取り付けられていることで、異常充電時の安全性をより高めることが可能である。感熱性の保護素子としては、ＰＴＣ、温度ヒューズ、サーミスタ、サーモスタットなどがあげられる。 In addition, the nonaqueous electrolyte secondary battery of the present invention can be further improved in safety during abnormal charging by attaching a heat-sensitive protective element in addition to the current interruption mechanism. Examples of the heat-sensitive protective element include a PTC, a thermal fuse, a thermistor, and a thermostat.
これらは単独で用いてもよく、組み合わせて用いても良い。特にＰＴＣ、サーミスタ、サーモスタットなどの復帰型の感熱性保護素子を電流遮断機構と併せて用いることが好ましい。この理由は以下の通りである。電流遮断機構のみを有する電池が異常充電された場合、電池の内圧上昇により電流遮断機構が作動するが、何らかの理由で電流遮断機構が作動する内圧に至るまでに時間がかかった場合、長時間に渡って異常充電が継続されることになる。 These may be used alone or in combination. In particular, it is preferable to use a reset type heat-sensitive protective element such as PTC, thermistor, thermostat or the like together with a current interruption mechanism. The reason is as follows. When a battery that has only a current interrupting mechanism is abnormally charged, the current interrupting mechanism operates due to an increase in the internal pressure of the battery, but if for some reason it takes time to reach the internal pressure at which the current interrupting mechanism operates, it takes a long time. Abnormal charging will continue across.
一方、復帰型の感熱性保護素子のみを有する電池が異常充電された場合、温度を感知することにより保護素子が作動し、充電電流は大幅に減少するが、時間が経つと充電電流が復帰するか、もしくは微小電流による充電が永遠と続くことになる。電流遮断機構と復帰型の感熱性保護素子が併せて用いられた電池の場合、異常充電時に何らかの理由で電流遮断機構が作動する内圧に至るまでに時間がかかった場合でも、感熱性保護素子が温度を感知することにより先行して作動し、充電電流は大幅に減少する。その後は微小電流で充電が継続されるために電池内部でのガス発生は継続して起こり、やがては電流遮断機構の作動圧力に到達して電流遮断機構が作動し、完全に充電電流を遮断することができる。 On the other hand, when a battery having only a reset-type heat-sensitive protection element is abnormally charged, the protection element is activated by sensing the temperature, and the charging current is greatly reduced, but the charging current is restored over time. Or charging with a minute current will last forever. In the case of a battery in which a current interrupting mechanism and a reset-type thermosensitive protective element are used in combination, even if it takes time to reach the internal pressure at which the current interrupting mechanism operates for some reason during abnormal charging, the thermosensitive protective element Operating in advance by sensing temperature, the charging current is greatly reduced. After that, since charging continues with a minute current, gas generation inside the battery continues, and eventually the operating pressure of the current interrupt mechanism is reached and the current interrupt mechanism operates to completely interrupt the charge current. be able to.
また、本発明の非水電解液二次電池を単数または複数使用した電池パックとすることも可能であり、その場合も上記と同様の感熱性の保護素子を取り付けることにより異常充電時の安全性を向上させた電池パックとすることができる。 In addition, a battery pack using one or a plurality of the non-aqueous electrolyte secondary batteries of the present invention can be used, and in that case, the safety during abnormal charging can be achieved by attaching a heat-sensitive protective element similar to the above. The battery pack can be improved.
以下、本発明を実施例に基づいて図面を参照しながら説明する。
《実施例１》
図１に本実施例で用いた円筒型非水電解液二次電池（直径１８ｍｍ、総高６５ｍｍ）の右半分断面正面図を示す。この電池は以下のように作製した。セパレータ１を介して、帯状正極板２と負極板３とを複数回渦巻状に捲回して、極板群を構成した。正極板２と負極板３にはそれぞれアルミニウム製正極リード４およびニッケル製負極リード５を溶接した。極板群の下にポリエチレン樹脂製底部絶縁板６を装着し、内面をニッケルメッキした鉄製電池ケース７内に収容し、負極リード５の他端を電池ケース７の内定面にスポット溶接した。極板群の上面にポリエチレン樹脂製上部絶縁板８を載置してから電池ケース７の開口部の所定位置に溝入れし、所定量の非水電解液を電池ケース７内に注入し、極板群に含浸させた。ポリプロピレン樹脂製ガスケット９を周縁部に装着させたステンレス鋼製の電流遮断機構内蔵封口板１０を準備し、その下面に正極リード４の他端をスポット溶接した。その後、電池ケース７の開口部に封口板１０装着し、電池ケース７の上縁部をガスケット９にかしめて開口部を封口し、電池を完成した。
Hereinafter, the present invention will be described based on examples with reference to the drawings.
Example 1
FIG. 1 shows a right half cross-sectional front view of a cylindrical nonaqueous electrolyte secondary battery (diameter 18 mm, total height 65 mm) used in this example. This battery was produced as follows. The strip-shaped positive electrode plate 2 and the negative electrode plate 3 were wound in a spiral shape through the separator 1 to constitute an electrode plate group. An aluminum positive electrode lead 4 and a nickel negative electrode lead 5 were welded to the positive electrode plate 2 and the negative electrode plate 3, respectively. A bottom insulating plate 6 made of polyethylene resin was mounted under the electrode plate group, the inner surface was accommodated in a nickel-plated iron battery case 7, and the other end of the negative electrode lead 5 was spot welded to the inner surface of the battery case 7. After placing the upper insulating plate 8 made of polyethylene resin on the upper surface of the electrode plate group, it is grooved at a predetermined position in the opening of the battery case 7, and a predetermined amount of nonaqueous electrolyte is injected into the battery case 7. The plate group was impregnated. A stainless steel sealing plate 10 with a built-in current interruption mechanism having a polypropylene resin gasket 9 attached to the peripheral edge thereof was prepared, and the other end of the positive electrode lead 4 was spot welded to the lower surface thereof. Thereafter, the sealing plate 10 was attached to the opening of the battery case 7, the upper edge of the battery case 7 was crimped to the gasket 9, and the opening was sealed to complete the battery.
正極板２は以下のように作製した。０．９５ｍｏｌ／リットルの濃度で硫酸コバルトを含み、０．０５ｍｏｌ／リットルの濃度で硫酸マグネシウムを含む水溶液を、反応槽に連続供給し、水のｐＨが１０〜１３になるように反応槽に水酸化ナトリウムを滴下しながら、活物質の前駆体を合成した。その結果、Ｃｏ0.95Ｍｇ0.05（ＯＨ）2からなる水酸化物を得た。
この前駆体と炭酸リチウムとを、リチウムとコバルトとマグネシウムとのモル比が、１：０．９５：０．０５になるように混合し、混合物を６００℃で１０時間仮焼成し、粉砕した。次いで、粉砕された焼成物を９００℃で再度１０時間焼成し、粉砕、分級し、一般式Ｌｉ（Ｃｏ0.95Ｍｇ0.05）Ｏ2で表される正極活物質を得た。１００質量部のＬｉ（Ｃｏ0.95Ｍｇ0.05）Ｏ2に、導電剤としてアセチレンブラック１．５質量部、結着剤として分子量３０００００のポリフッ化ビニリデン（ＰＶｄＦ）のＮ−メチル−２−ピロリドン溶液を樹脂分で２質量部加え、攪拌・混合してペースト状正極合剤を得た。そして、厚さ１５μｍのアルミニウム箔製集電体の両面に前記ペースト状正極合剤を塗布し、乾燥後、圧延ローラーを用いて圧延を行い、所定寸法に裁断して正極板２とした。
The positive electrode plate 2 was produced as follows. An aqueous solution containing cobalt sulfate at a concentration of 0.95 mol / liter and containing magnesium sulfate at a concentration of 0.05 mol / liter is continuously supplied to the reaction vessel, and water is added to the reaction vessel so that the pH of the water becomes 10-13. While adding sodium oxide dropwise, an active material precursor was synthesized. As a result, a hydroxide composed of Co 0.95 Mg 0.05 (OH) 2 was obtained.
This precursor and lithium carbonate were mixed so that the molar ratio of lithium, cobalt and magnesium was 1: 0.95: 0.05, and the mixture was calcined at 600 ° C. for 10 hours and pulverized. Next, the pulverized fired product was fired again at 900 ° C. for 10 hours, pulverized, and classified to obtain a positive electrode active material represented by the general formula Li (Co 0.95 Mg 0.05 ) O 2 . 100 parts by mass of Li (Co 0.95 Mg 0.05 ) O 2 was resinized with 1.5 parts by mass of acetylene black as a conductive agent and an N-methyl-2-pyrrolidone solution of polyvinylidene fluoride (PVdF) having a molecular weight of 300,000 as a binder. 2 parts by mass were added, and the mixture was stirred and mixed to obtain a paste-like positive electrode mixture. And the said paste-form positive mix was apply | coated to both surfaces of the 15-micrometer-thick aluminum foil collector, and after drying, it rolled using the rolling roller, it cut | judged to the predetermined dimension, and was set as the positive electrode plate 2. FIG.
負極板３は以下のように作製した。平均粒径が約２０μｍになるように粉砕・分級した鱗片状黒鉛１００質量部と、結着剤のスチレン−ブタジエンゴム３質量部とを混合した後、１質量％カルボキシメチルセルロース水溶液１００質量部を加え、攪拌・混合してペースト状負極合剤を得た。そして、厚さ１０μｍの銅箔製集電体の両面に前記ペースト状負極合剤を塗布し、乾燥後、圧延ローラーを用いて圧延を行い、所定寸法に裁断して負極板３とした。 The negative electrode plate 3 was produced as follows. After mixing 100 parts by mass of flaky graphite pulverized and classified so that the average particle size becomes about 20 μm and 3 parts by mass of styrene-butadiene rubber as a binder, 100 parts by mass of 1% by mass carboxymethylcellulose aqueous solution was added. The mixture was stirred and mixed to obtain a paste-like negative electrode mixture. And the said paste-form negative electrode mixture was apply | coated on both surfaces of the 10-micrometer-thick copper foil collector, and after drying, it rolled using the rolling roller, it cut | judged to the predetermined dimension, and was set as the negative electrode plate 3.
前述のように作製した帯状の正極板２、負極板３および厚さ２５μｍの微多孔性ポリエチレン樹脂製セパレータ１を用いて上記極板群を構成した。非水電解液としてγ−ブチロラクトンとビニレンカーボネートとエチレンカーボネートの体積比８０：２：１８の混合溶媒に１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いた。このようにして作製した電池を本発明の電池１とした。 The above-described electrode plate group was configured using the strip-like positive electrode plate 2, the negative electrode plate 3 and the microporous polyethylene resin separator 1 having a thickness of 25 μm prepared as described above. As the non-aqueous electrolyte, a solution obtained by dissolving LiPF 6 at a concentration of 1.0 mol / liter in a mixed solvent of γ-butyrolactone, vinylene carbonate, and ethylene carbonate in a volume ratio of 80: 2: 18 was used. The battery thus produced was designated as battery 1 of the present invention.
《実施例２》
非水電解液としてγ−ブチロラクトンとビニレンカーボネートとエチレンカーボネートとジエチルカーボネートの体積比７０：２：１８：１０の混合溶媒に１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いたこと以外実施例１と同様に本発明の電池２を作製した。
Example 2
Other than using non-aqueous electrolyte solution in which LiPF 6 was dissolved at a concentration of 1.0 mol / liter in a mixed solvent of γ-butyrolactone, vinylene carbonate, ethylene carbonate and diethyl carbonate in a volume ratio of 70: 2: 18: 10 A battery 2 of the present invention was produced in the same manner as in Example 1.
《実施例３》
非水電解液としてγ−ブチロラクトンとビニレンカーボネートとエチレンカーボネートとジエチルカーボネートとシクロヘキシルベンゼンの体積比６８：２：１８：１０：２の混合溶媒に１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いたこと以外実施例１と同様に本発明の電池３を作製した。
Example 3
LiPF 6 dissolved in a mixed solvent of γ-butyrolactone, vinylene carbonate, ethylene carbonate, diethyl carbonate, and cyclohexylbenzene in a volume ratio of 68: 2: 18: 10: 2 at a concentration of 1.0 mol / liter as a non-aqueous electrolyte A battery 3 of the present invention was produced in the same manner as in Example 1 except that was used.
《実施例４》
非水電解液としてγ−ブチロラクトンとビニレンカーボネートとエチレンカーボネートとジエチルカーボネートとジフェニルエーテルの体積比６８：２：１８：１０：２の混合溶媒に１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いたこと以外実施例１と同様に本発明の電池４を作製した。
Example 4
A nonaqueous electrolytic solution in which LiPF 6 is dissolved at a concentration of 1.0 mol / liter in a mixed solvent of γ-butyrolactone, vinylene carbonate, ethylene carbonate, diethyl carbonate, and diphenyl ether in a volume ratio of 68: 2: 18: 10: 2 A battery 4 of the present invention was produced in the same manner as in Example 1 except that it was used.
《実施例５》
非水電解液としてγ−ブチロラクトンとビニレンカーボネートとエチレンカーボネートの体積比８０：２：１８の混合溶媒に合計１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６とＬｉＢＦ４を１：１の比率で溶解したものを用いたこと以外実施例１と同様に本発明の電池５を作製した。
Example 5
LiPF 6 and LiBF 4 dissolved at a ratio of 1: 1 in a mixed solvent of γ-butyrolactone, vinylene carbonate and ethylene carbonate in a volume ratio of 80: 2: 18 at a total concentration of 1.0 mol / liter as a non-aqueous electrolyte A battery 5 of the present invention was produced in the same manner as in Example 1 except that was used.
《実施例６》
平均粒径２０μｍの燐片状黒鉛を、石油ピッチと混合し、８００℃で焼成し、燐片状黒鉛の表面の少なくとも一部を非晶質炭素で被覆した。こうして得られた炭素材料（平均粒径２２μｍ）を、鱗片状黒鉛の代わりに用いたこと以外実施例１と同様に本発明の電池６を作製した。
Example 6
The flake graphite having an average particle diameter of 20 μm was mixed with petroleum pitch and fired at 800 ° C., and at least a part of the surface of the flake graphite was coated with amorphous carbon. A battery 6 of the present invention was produced in the same manner as in Example 1 except that the carbon material (average particle size 22 μm) thus obtained was used instead of scaly graphite.
《実施例７》
非水電解液としてγ−ブチロラクトンに１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いたこと以外実施例１と同様に本発明の電池７を作製した。
Example 7
A battery 7 of the present invention was produced in the same manner as in Example 1 except that a non-aqueous electrolyte solution using LiPF 6 dissolved in γ-butyrolactone at a concentration of 1.0 mol / liter was used.
《比較例１》
マグネシウムを含まない一般式ＬｉＣｏＯ2で示される正極活物質を用いたこと以外実施例１と同様に比較例の電池１を作製した。
<< Comparative Example 1 >>
A comparative battery 1 was prepared in the same manner as in Example 1 except that the positive electrode active material represented by the general formula LiCoO 2 not containing magnesium was used.
《比較例２》
非水電解液としてエチルメチルカーボネートとエチレンカーボネートの体積比８０：２０の混合溶媒に１．０ｍｏｌ／リットルの濃度でＬｉＰＦ６を溶解したものを用いたこと以外実施例１と同様に比較例の電池２を作製した。
<< Comparative Example 2 >>
A battery of a comparative example as in Example 1 except that a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1.0 mol / liter in a mixed solvent of ethyl methyl carbonate and ethylene carbonate in a volume ratio of 80:20. 2 was produced.
《比較例３》
実施例１に準じて、前駆体としてＣｏ0.998Ｍｇ0.002（ＯＨ）2からなる水酸化物を合成した。この前駆体と炭酸リチウムとを、リチウムとコバルトとマグネシウムとのモル比が、１：０．９９８：０．００２になるように混合したこと以外、実施例１と同様の操作を行って、一般式Ｌｉ（Ｃｏ0.998Ｍｇ0.002）Ｏ2で表される正極活物質を得た。次いで、この正極活物質を用いたこと以外、実施例１と同様にして、比較例の電池３を作製した。
<< Comparative Example 3 >>
In accordance with Example 1, a hydroxide composed of Co 0.998 Mg 0.002 (OH) 2 as a precursor was synthesized. The same procedure as in Example 1 was performed except that this precursor and lithium carbonate were mixed so that the molar ratio of lithium, cobalt, and magnesium was 1: 0.998: 0.002. A positive electrode active material represented by the formula Li (Co 0.998 Mg 0.002 ) O 2 was obtained. Next, a comparative battery 3 was produced in the same manner as in Example 1 except that this positive electrode active material was used.
《比較例４》
実施例１に準じて、前駆体としてＣｏ0.80Ｍｇ0.20（ＯＨ）2からなる水酸化物を合成した。この前駆体と炭酸リチウムとを、リチウムとコバルトとマグネシウムとのモル比が、１：０．８０：０．２０になるように混合したこと以外、実施例１と同様の操作を行って、一般式Ｌｉ（Ｃｏ0.80Ｍｇ0.20）Ｏ2で表される正極活物質を得た。次いで、この正極活物質を用いたこと以外、実施例１と同様にして、比較例の電池４を作製した。
<< Comparative Example 4 >>
According to Example 1, a hydroxide composed of Co 0.80 Mg 0.20 (OH) 2 as a precursor was synthesized. The same procedure as in Example 1 was performed except that this precursor and lithium carbonate were mixed so that the molar ratio of lithium, cobalt, and magnesium was 1: 0.80: 0.20. A positive electrode active material represented by the formula Li (Co 0.80 Mg 0.20 ) O 2 was obtained. Subsequently, the battery 4 of the comparative example was produced like Example 1 except having used this positive electrode active material.
［電池の評価］
実施例１〜８および比較例１〜４で作製した電池、各１０セルを用いて、充放電サイクル特性、低温放電特性、高温保存時の電流遮断機構の作動までの時間測定、過充電特性、高温保存特性を下記の評価方法により評価したときの平均値を算出し、比較を行った。
[Battery evaluation]
Using the batteries prepared in Examples 1 to 8 and Comparative Examples 1 to 4 and 10 cells each, charge and discharge cycle characteristics, low temperature discharge characteristics, time measurement until operation of the current interruption mechanism during high temperature storage, overcharge characteristics, An average value when the high temperature storage characteristics were evaluated by the following evaluation method was calculated and compared.
（１）充放電サイクル特性
電池の充放電サイクルを繰り返し、３サイクル目の容量を１００％として容量が５０％になった時点のサイクル数をサイクル寿命とみなした。なお、充電は、環境温度２０℃で、上限電圧を４．２Ｖに設定して、最大電流１０５０ｍＡで２時間３０分間定電流・定電圧充電を行った。放電は、この充電状態の電池を環境温度２０℃で、放電電流１５００ｍＡ、放電終止電位３．０Ｖの定電流放電を行った。その結果を表１に示す。
(1) Charging / discharging cycle characteristics The charging / discharging cycle of the battery was repeated, and the capacity at the third cycle was defined as 100%, and the cycle number when the capacity reached 50% was regarded as the cycle life. The charging was performed at a constant current / constant voltage for 2 hours and 30 minutes at a maximum current of 1050 mA at an environmental temperature of 20 ° C. and an upper limit voltage of 4.2 V. For discharging, the charged battery was subjected to constant current discharge at an environmental temperature of 20 ° C., a discharge current of 1500 mA, and a discharge end potential of 3.0 V. The results are shown in Table 1.
（２）低温放電特性
電池の低温環境下における放電特性を比較した。この試験において、充電は、環境温度２０℃で、上限電圧を４．２Ｖに設定して、最大電流１０５０ｍＡで２時間３０分間定電流・定電圧充電を行った。放電は、この充電状態の電池を環境温度２０℃と−２０℃で、放電電流１５００ｍＡ、放電終止電位３．０Ｖの定電流放電を行った。２０℃における放電容量に対する−２０℃における放電容量の割合を百分率（％）で求め、低温環境下での容量維持率とした。その結果を表１に示す。
(2) Low temperature discharge characteristics The discharge characteristics of the batteries in a low temperature environment were compared. In this test, charging was performed at a constant current / constant voltage at an environmental temperature of 20 ° C., an upper limit voltage of 4.2 V, and a maximum current of 1050 mA for 2 hours 30 minutes. For discharging, the charged battery was subjected to constant current discharge at an environmental temperature of 20 ° C. and −20 ° C. with a discharge current of 1500 mA and a discharge end potential of 3.0V. The ratio of the discharge capacity at −20 ° C. to the discharge capacity at 20 ° C. was obtained as a percentage (%), and was defined as the capacity maintenance rate under a low temperature environment. The results are shown in Table 1.
（３）高温保存時の電流遮断機構の作動までの時間測定
環境温度２０℃で上限電圧を４．２Ｖに設定して、最大電流１０５０ｍＡで２時間３０分間定電流・定電圧充電を行った電池を、８５℃の環境下に保存し、ガス発生により電流遮断機構が誤作動するまでの時間を測定した。最長２４０時間まで試験を継続した。その結果を表１に示す。
(3) Time measurement until operation of current interruption mechanism during high temperature storage Battery with constant current / constant voltage charging for 2 hours 30 minutes at maximum temperature of 1050 mA with upper limit voltage set to 4.2 V at 20 ° C Was stored in an environment of 85 ° C., and the time until the current interruption mechanism malfunctioned due to gas generation was measured. The test was continued for up to 240 hours. The results are shown in Table 1.
（４）過充電特性
環境温度２０℃で電流値１５００ｍＡの条件で５時間連続して充電を行い、電池表面の最大温度を測定した。その結果を表１に示す。
(4) Overcharge characteristics The battery was continuously charged for 5 hours under the condition of an ambient temperature of 20 ° C. and a current value of 1500 mA, and the maximum temperature of the battery surface was measured. The results are shown in Table 1.
（５）高温保存特性
環境温度２０℃で、上限電圧を４．２Ｖに設定して、最大電流１０５０ｍＡで２時間３０分間定電流・定電圧充電を行った後、電流１５００ｍＡｈ、放電終止電圧３．０Ｖの放電を行う条件の充放電を２サイクル行い、２サイクル目の放電容量を確認した。その後、充電状態の電池を６０℃で３日間保存した。次いで、保存後の電池を再び２０℃で、上記と同一条件で２サイクル充放電し、高温保存後の容量維持率を求めた。保存前の放電容量を１００とした場合の、高温保存後２サイクル目の放電容量の割合を百分率（％）で求め、それを容量維持率とした。その結果を表１に示す。
(5) High temperature storage characteristics After setting the upper limit voltage to 4.2 V at an environmental temperature of 20 ° C. and performing constant current / constant voltage charging at a maximum current of 1050 mA for 2 hours and 30 minutes, a current of 1500 mAh and a discharge end voltage of 3. Two cycles of charging / discharging under the condition of discharging at 0 V were performed, and the discharge capacity at the second cycle was confirmed. Thereafter, the charged battery was stored at 60 ° C. for 3 days. Next, the battery after storage was charged and discharged for 2 cycles again at 20 ° C. under the same conditions as described above, and the capacity retention rate after storage at high temperature was determined. When the discharge capacity before storage was set to 100, the ratio of the discharge capacity at the second cycle after high-temperature storage was obtained as a percentage (%), and this was used as the capacity maintenance ratio. The results are shown in Table 1.
表１において、本発明の電池１〜７と、比較例の電池１の充放電サイクル特性の比較より、マグネシウムを添加した正極活物質を用いることにより、充放電サイクル特性が大幅に向上することが解る。特にＬｉＰＦ６とＬｉＢＦ４の混合溶質を用いた本発明の電池５はさらなるサイクル特性の改善が認められた。 In Table 1, from the comparison of the charge / discharge cycle characteristics of the batteries 1 to 7 of the present invention and the battery 1 of the comparative example, the charge / discharge cycle characteristics can be greatly improved by using the positive electrode active material added with magnesium. I understand. In particular, the battery 5 of the present invention using a mixed solute of LiPF 6 and LiBF 4 was found to have further improved cycle characteristics.
マグネシウムの添加量が過少である比較例の電池３は、マグネシウムを添加しない比較例の電池１と同等のサイクル特性しか得られなかった。また、マグネシウムの添加量が過多の比較例の電池４は、初期の容量が低く、高温保存時の容量維持率も５１％と低かった。 The battery 3 of the comparative example in which the addition amount of magnesium was too small could only obtain cycle characteristics equivalent to those of the battery 1 of the comparative example in which no magnesium was added. Moreover, the battery 4 of the comparative example in which the additive amount of magnesium was excessive had a low initial capacity and a low capacity retention rate of 51% during high-temperature storage.
ジエチルカーボネートを含有する非水電解液を用いた本発明の電池２、３および４は、本発明の電池１に比べて低温放電特性の向上が認められた。非水溶媒中にジエチルカーボネートを含有させることにより非水溶媒の粘度が低下し、低温時の電池の充放電特性が改善されたと考えられる。 The batteries 2, 3 and 4 of the present invention using a non-aqueous electrolyte containing diethyl carbonate were found to have improved low-temperature discharge characteristics as compared with the battery 1 of the present invention. By including diethyl carbonate in the non-aqueous solvent, it is considered that the viscosity of the non-aqueous solvent is lowered and the charge / discharge characteristics of the battery at low temperature are improved.
本発明の電池１〜７と、比較例の電池２の高温保存時の電流遮断機構の作動までの時間測定の比較より、非水電解液中にγ−ブチロラクトンを含有することにより、大幅にガス発生が抑制され、電流遮断機構が作動するまでの時間が大きく伸びていることが解る。これは、γ−ブチロラクトンが正極表面で分解して分解物が正極表面に緻密な被膜を形成し、電解液と正極との直接の接触を抑制する結果、高温保存時のガス発生を大幅に抑制しているためである。また、非水電解液中にγ−ブチロラクトン以外にビニレンカーボネートとエチレンカーボネートを含有しない本発明の電池７に比べて、非水電解液中にγ−ブチロラクトン、ビニレンカーボネート及びエチレンカーボネートを含有する本発明の電池１は、高温保存特性の容量維持率の向上が認められた。これは、本発明の電池１では非水電解液中にγ−ブチロラクトンと併せてビニレンカーボネートとエチレンカーボネートを含有することで、ビニレンカーボネートが負極上で連鎖的に重合反応を起こし、迅速に負極上に緻密で強固な被膜を形成することで、γ−ブチロラクトンの一部が負極表面で分解されるのを抑制し、さらにエチレンカーボネートが、高温環境下でビニレンカーボネートの分解が促進されて負極表面に過剰な被膜が形成されるのを防ぐことにより、高温保存特性の向上が認められたと考えられる。 From the comparison of the time measurement until the operation of the current interruption mechanism at the time of high-temperature storage of the batteries 1 to 7 of the present invention and the battery 2 of the comparative example, by containing γ-butyrolactone in the non-aqueous electrolyte, gas is greatly increased. It can be seen that the time until the occurrence of the current interruption mechanism is suppressed is greatly increased. This is because γ-butyrolactone decomposes on the surface of the positive electrode and the decomposed product forms a dense film on the surface of the positive electrode, suppressing direct contact between the electrolyte and the positive electrode, greatly reducing gas generation during high-temperature storage. It is because it is doing. Further, the present invention contains γ-butyrolactone, vinylene carbonate, and ethylene carbonate in the non-aqueous electrolyte as compared with the battery 7 of the present invention that does not contain vinylene carbonate and ethylene carbonate other than γ-butyrolactone in the non-aqueous electrolyte. In the battery 1, an improvement in capacity retention rate of high-temperature storage characteristics was observed. This is because, in the battery 1 of the present invention, vinylene carbonate and ethylene carbonate are contained in the non-aqueous electrolyte together with γ-butyrolactone so that vinylene carbonate causes a polymerization reaction in a chain on the negative electrode, and quickly on the negative electrode. By forming a dense and strong film, it is possible to suppress the decomposition of a part of γ-butyrolactone on the negative electrode surface, and further, ethylene carbonate promotes the decomposition of vinylene carbonate in a high temperature environment, and on the negative electrode surface. It is considered that an improvement in high-temperature storage characteristics was recognized by preventing the formation of an excessive film.
また、非水電解液中にシクロヘキシルベンゼンとジフェニルエーテルを含有する本発明の電池３、４では、過充電試験における最大温度が大幅に低下していることが解る。 Moreover, in the batteries 3 and 4 of the present invention containing cyclohexylbenzene and diphenyl ether in the non-aqueous electrolyte, it can be seen that the maximum temperature in the overcharge test is greatly reduced.
燐片状黒鉛の表面の少なくとも一部を非晶質炭素で被覆した負極活物質を用いた本発明の電池６では、高温保存特性の容量維持率で向上が認められた。これは負極表面を非晶質炭素で被覆することにより、高温保存時の電解液の分解が抑制されたためと考えられる。 In the battery 6 of the present invention using the negative electrode active material in which at least a part of the surface of the flake graphite was coated with amorphous carbon, an improvement was observed in the capacity retention rate of the high temperature storage characteristics. This is presumably because the decomposition of the electrolyte during high temperature storage was suppressed by coating the negative electrode surface with amorphous carbon.
本発明の非水電解液二次電池及び非水電解液二次電池パックは、サイクル特性に優れ、且つ電池を高温条件下に一定時間放置しても電流遮断機構が誤作動を起こさないので、パソコンおよび携帯電話等の電子機器の駆動用電源等として有用である。 The non-aqueous electrolyte secondary battery and the non-aqueous electrolyte secondary battery pack of the present invention are excellent in cycle characteristics and the current interruption mechanism does not malfunction even if the battery is left for a certain period of time under high temperature conditions. It is useful as a power source for driving electronic devices such as personal computers and mobile phones.
１ セパレータ
２ 正極板
３ 負極板
４ 正極リード
５ 負極リード
６ 底部絶縁板
７ 電池ケース
８ 上部絶縁板
９ ガスケット
１０ 封口板
DESCRIPTION OF SYMBOLS 1 Separator 2 Positive electrode plate 3 Negative electrode plate 4 Positive electrode lead 5 Negative electrode lead 6 Bottom insulating plate 7 Battery case 8 Upper insulating plate 9 Gasket 10 Sealing plate
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| JP2011527090A (en) * | 2008-07-03 | 2011-10-20 | ボード オブ ガバナーズ フォー ハイヤー エデュケーション， ステート オブ ロード アイランド アンド プロヴィデンス プランテーションズ | Inhibition of oxidation of lithium ion battery electrolytes by electrolyte additives |
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| JP2009541938A (en) * | 2006-06-23 | 2009-11-26 | ボストン−パワー，インコーポレイテッド | Lithium ion secondary battery |
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