JP2012054067A - Nonaqueous electrolytic secondary battery - Google Patents
Nonaqueous electrolytic secondary battery Download PDFInfo
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- JP2012054067A JP2012054067A JP2010194840A JP2010194840A JP2012054067A JP 2012054067 A JP2012054067 A JP 2012054067A JP 2010194840 A JP2010194840 A JP 2010194840A JP 2010194840 A JP2010194840 A JP 2010194840A JP 2012054067 A JP2012054067 A JP 2012054067A
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- JP
- Japan
- Prior art keywords
- active material
- positive electrode
- electrode active
- lithium
- secondary battery
- 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
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- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 62
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims description 135
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 34
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 34
- -1 lithium transition metal Chemical class 0.000 claims description 30
- 239000010419 fine particle Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 19
- 239000002905 metal composite material Substances 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 12
- 239000006183 anode active material Substances 0.000 abstract 5
- 239000011859 microparticle Substances 0.000 abstract 4
- 235000012054 meals Nutrition 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 2
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical compound [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000006182 cathode active material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 33
- 238000007600 charging Methods 0.000 description 16
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000007774 longterm Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 6
- LWHHUEHWVBVASY-UHFFFAOYSA-N erbium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LWHHUEHWVBVASY-UHFFFAOYSA-N 0.000 description 6
- 229910052691 Erbium Inorganic materials 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 5
- 150000002123 erbium compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 150000003755 zirconium compounds Chemical class 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000005678 chain carbonates Chemical class 0.000 description 3
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- 238000010828 elution Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
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- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-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
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- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- RCWAXFGXJSYOSZ-UHFFFAOYSA-N erbium;trihydrate Chemical compound O.O.O.[Er] RCWAXFGXJSYOSZ-UHFFFAOYSA-N 0.000 description 2
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 150000002798 neodymium compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 150000003317 samarium compounds Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HMXHUUDRVBXHBQ-UHFFFAOYSA-N (2-hydroxyacetyl) 2-hydroxyacetate Chemical compound OCC(=O)OC(=O)CO HMXHUUDRVBXHBQ-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
- NZPSDGIEKAQVEZ-UHFFFAOYSA-N 1,3-benzodioxol-2-one Chemical compound C1=CC=CC2=C1OC(=O)O2 NZPSDGIEKAQVEZ-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- VUAXHMVRKOTJKP-UHFFFAOYSA-M 2,2-dimethylbutanoate Chemical compound CCC(C)(C)C([O-])=O VUAXHMVRKOTJKP-UHFFFAOYSA-M 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO 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
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 102000005717 Myeloma Proteins Human genes 0.000 description 1
- 108010045503 Myeloma Proteins Proteins 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- HFZQESHWPLWNSE-UHFFFAOYSA-K [Li+].P(O)(O)(O)=O.P(=O)([O-])([O-])[O-].[Li+].[Li+] Chemical compound [Li+].P(O)(O)(O)=O.P(=O)([O-])([O-])[O-].[Li+].[Li+] HFZQESHWPLWNSE-UHFFFAOYSA-K 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BPFOYPDHLJUICH-UHFFFAOYSA-N ethenyl ethyl carbonate Chemical compound CCOC(=O)OC=C BPFOYPDHLJUICH-UHFFFAOYSA-N 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002641 lithium Chemical class 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
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- 230000001629 suppression Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、非水電解質二次電池に関し、特に正極活物質表面に希土類元素化合物からなる微粒子が付着した、高容量で連続充電保存特性及びサイクル特性に優れた非水電解質二次電池に関する。 The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolyte secondary battery having a high capacity and excellent continuous charge storage characteristics and cycle characteristics, in which fine particles made of a rare earth element compound adhere to the surface of a positive electrode active material.
今日の携帯電話機、携帯型パーソナルコンピューター、携帯型音楽プレイヤー等の携帯型電子機器の駆動電源として、さらには、ハイブリッド電気自動車（ＨＥＶ）や電気自動車（ＥＶ）用の電源として、高エネルギー密度を有し、高容量である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が広く利用されている。 It has high energy density as a drive power source for portable electronic devices such as today's mobile phones, portable personal computers and portable music players, and also as a power source for hybrid electric vehicles (HEV) and electric vehicles (EV). However, non-aqueous electrolyte secondary batteries represented by high-capacity lithium ion secondary batteries are widely used.
これらの非水電解質二次電池の正極活物質としては、リチウムイオンを可逆的に吸蔵・放出することが可能なＬｉＭＯ２（但し、ＭはＣｏ、Ｎｉ、Ｍｎの少なくとも１種である）で表されるリチウム遷移金属複合酸化物、すなわち、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉｙＣｏ１−ｙＯ２（ｙ＝０．０１〜０．９９）、ＬｉＭｎＯ２、ＬｉＣｏｘＭｎｙＮｉｚＯ２（ｘ＋ｙ＋ｚ＝１）や、ＬｉＭｎ２Ｏ４又はＬｉＦｅＰＯ４などが一種単独もしくは複数種を混合して用いられている。また、負極活物質としては、黒鉛等の炭素材料や、Ｓｉ又はＳｎ等のリチウムと合金化する材料などが用いられている。 The positive electrode active material of these nonaqueous electrolyte secondary batteries is represented by LiMO 2 (where M is at least one of Co, Ni, and Mn) capable of reversibly occluding and releasing lithium ions. lithium transition metal composite oxide to be, namely, LiCoO 2, LiNiO 2, LiNi y Co 1-y O 2 (y = 0.01~0.99), LiMnO 2, LiCo x Mn y Ni z O 2 (x + y + z = 1) and, like LiMn 2 O 4 or LiFePO 4 is used as a mixture of one kind alone or in combination. In addition, as the negative electrode active material, a carbon material such as graphite or a material alloyed with lithium such as Si or Sn is used.
このうち、特に各種電池特性が他のものに対して優れていることから、リチウムコバルト複合酸化物や異種金属元素添加リチウムコバルト複合酸化物が多く使用されている。しかしながら、コバルトは高価であると共に資源としての存在量が少ない。そのため、これらのリチウムコバルト複合酸化物や異種金属元素添加リチウムコバルト複合酸化物を非水電解質二次電池の正極活物質として使用し続けるには非水電解質二次電池のさらなる高性能化が望まれている。 Among these, since various battery characteristics are particularly excellent with respect to others, lithium cobalt composite oxides and heterogeneous metal element-added lithium cobalt composite oxides are often used. However, cobalt is expensive and has a small abundance as a resource. Therefore, in order to continue using these lithium cobalt composite oxides and lithium cobalt composite oxides containing different metal elements as positive electrode active materials for non-aqueous electrolyte secondary batteries, further enhancement of the performance of non-aqueous electrolyte secondary batteries is desired. ing.
特に、近年の移動情報端末における動画再生、ゲーム機能といった娯楽機能の充実に伴う消費電力の増大化及びＨＥＶやＥＶの長時間駆動の要望から、非水電解質二次電池のさらなる高容量化が要求されている。非水電解質二次電池を高容量化する方策としては、
（１）活物質の容量を高くする、
（２）充電電圧を高くする、
（３）活物質の充填量を増やし充填密度を高くする、
などの方法が考えられる。しかしながら特に、充電電圧を高くした場合、具体的には正極の充電電位をリチウム基準で４．３Ｖよりも高くした場合、非水電解液が分解しやすくなり、高温で保存したり、連続充電した場合に、電解液が分解してガス発生し、電池が膨らんだり、電池の内部圧力が大きくなるという問題を生じる。
In particular, non-aqueous electrolyte secondary batteries are required to have higher capacities due to demands for increased power consumption and long-term driving of HEVs and EVs with enhancement of entertainment functions such as video playback and game functions in recent mobile information terminals. Has been. As a measure to increase the capacity of non-aqueous electrolyte secondary batteries,
(1) Increase the capacity of the active material,
(2) Increase the charging voltage,
(3) Increase the filling amount of the active material to increase the filling density,
Such a method is conceivable. However, in particular, when the charging voltage is increased, specifically, when the charging potential of the positive electrode is higher than 4.3 V on the basis of lithium, the nonaqueous electrolytic solution is easily decomposed and stored at a high temperature or continuously charged. In some cases, the electrolytic solution is decomposed to generate gas, and the battery swells or the internal pressure of the battery increases.
また、正極上で酸化分解した分解物は、負極上に堆積してリチウムの受入性を阻害するため、負極の放電性能が低下するという問題点が存在する。特に、電池を高温、高電圧で使用する場合に、その問題点が顕著なものとなる。 Further, the decomposition product oxidized and decomposed on the positive electrode is deposited on the negative electrode and inhibits the acceptability of lithium, so that the discharge performance of the negative electrode is deteriorated. In particular, when the battery is used at a high temperature and a high voltage, the problem becomes remarkable.
下記特許文献１には、リチウム遷移金属複合酸化物の表面に希土類水酸化物・オキシ水酸化物の微粒子を分散した状態で付着させた正極活物質を用いることで、高温で充電保存した時の電解液分解反応を抑制し、電池膨れを抑制することができることが示されている。また、下記特許文献２には、正極活物質が、Ｍｇ、Ａｌ、Ｔｉ、Ｚｒの少なくとも一種が添加されたコバルト酸リチウムを含み、この正極活物質に、リン酸リチウムを添加することで、コバルト酸リチウムと非水電解質との反応を抑制し、正極の充電電位がリチウム基準で４．３Ｖ以上の電池における高温保存特性とサイクル特性を改善することができることが示されている。さらに、下記特許文献３には、正極活物質にＬｉｘＭＯ２を用い、電解質として６フッ化リン酸リチウムを用いると共に、正極中にリン酸リチウムを加えることで、高温保存特性とサイクル特性に優れる電池が得られることが示されている。 Patent Document 1 below uses a positive electrode active material in which rare earth hydroxide and oxyhydroxide fine particles are dispersed in the surface of a lithium transition metal composite oxide, which is used when charged and stored at a high temperature. It has been shown that the electrolyte decomposition reaction can be suppressed and battery swelling can be suppressed. Further, in Patent Document 2 below, the positive electrode active material includes lithium cobaltate to which at least one of Mg, Al, Ti, and Zr is added. By adding lithium phosphate to the positive electrode active material, cobalt is obtained. It has been shown that the reaction between lithium acid and a non-aqueous electrolyte can be suppressed, and the high-temperature storage characteristics and cycle characteristics of a battery having a positive electrode charging potential of 4.3 V or higher based on lithium can be improved. Furthermore, in Patent Document 3 below, Li x MO 2 is used as a positive electrode active material, lithium hexafluorophosphate is used as an electrolyte, and lithium phosphate is added to the positive electrode, so that high temperature storage characteristics and cycle characteristics can be obtained. It has been shown that excellent batteries can be obtained.
特許文献１：ＷＯ２０１０／００４９７３号公報
特許文献２：特開２００８−１２３９７２号公報
特許文献３：特開平 ９−３０６５４７号公報
Patent Document 1: WO 2010/004973 Patent Document 2: JP 2008-123972 A Patent Document 3: JP 9-306547 A
しかしながら、上記特許文献１に示されているように、非水電解質二次電池の正極として、正極活物質表面を希土類元素の化合物で被覆したものを用いると、高温サイクル時の容量維持率が低下するという課題があった。これは、充放電サイクルで劣化し難い正極と劣化しやすい負極との間でサイクルに伴い、充放電性能のバランスが崩れてしまうことが原因と考えられる。このように正負極間の充放電性能のバランスが崩れてしまうと、正極に比べて負極の充放電時の分極が大きくなり、負極の劣化が促進されてしまうからである。 However, as shown in Patent Document 1 above, when a positive electrode of a non-aqueous electrolyte secondary battery having a positive electrode active material surface coated with a rare earth element compound is used, the capacity retention rate during a high-temperature cycle is reduced. There was a problem to do. This is considered to be because the balance of charge / discharge performance is lost due to the cycle between the positive electrode which is hardly deteriorated in the charge / discharge cycle and the negative electrode which is easily deteriorated. This is because if the balance between the charge and discharge performance between the positive and negative electrodes is lost, the polarization during charge and discharge of the negative electrode becomes larger than that of the positive electrode, and the deterioration of the negative electrode is promoted.
なお、上記特許文献２及び３に示されているように、正極活物質中にリン酸リチウムを加えると、高温保温特性及びサイクル特性に優れた非水電解質二次電池が得られるが、正極の充電電位をリチウム基準で４．３Ｖ以上に高めた際の非水電解液の分解抑制効果は不十分であり、充電状態で高温で保存した場合に電池が膨れるという課題があった。 As shown in Patent Documents 2 and 3, when lithium phosphate is added to the positive electrode active material, a nonaqueous electrolyte secondary battery excellent in high temperature heat retention characteristics and cycle characteristics can be obtained. The effect of suppressing the decomposition of the non-aqueous electrolyte when the charging potential is increased to 4.3 V or more on the basis of lithium is insufficient, and there is a problem that the battery swells when stored at a high temperature in a charged state.
本発明は、上述のような従来技術の問題点を解決すべくなされたものであり、非水電解質二次電池の正極として正極活物質表面を希土類元素の化合物で被覆したものを用いた場合であっても、正極電位がリチウム基準で４．３Ｖ以上になるまで充電した際の電解液の分解抑制効果に優れ、高温下での連続充電時のガス発生を抑制し、かつサイクル特性が向上した非水電解質二次電池を提供することを目的とする。 The present invention has been made in order to solve the above-described problems of the prior art, and is a case where a positive electrode active material surface coated with a rare earth element compound is used as a positive electrode of a non-aqueous electrolyte secondary battery. Even when the positive electrode potential is 4.3 V or higher with respect to lithium, it is excellent in the effect of suppressing decomposition of the electrolyte, suppresses gas generation during continuous charging at high temperature, and improves cycle characteristics. An object is to provide a nonaqueous electrolyte secondary battery.
上記目的を達成するため、本発明の非水電解質二次電池は、正極活物質を有する正極と、負極活物質を有する負極と、セパレータと、非水電解質とを備える非水電解質二次電池において、前記正極は、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子が付着している正極活物質Ａと、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の化合物の微粒子が付着していない正極活物質Ｂと、
リン酸リチウムと、
を含んでいることを特徴とする。
In order to achieve the above object, a nonaqueous electrolyte secondary battery of the present invention is a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a separator, and a nonaqueous electrolyte. The positive electrode is
A lithium transition metal composite oxide containing lithium and cobalt and having a layered structure, the surface of which is coated with fine particles of at least one of a rare earth hydroxide and an oxyhydroxide Substance A;
A positive electrode active material B containing lithium and cobalt and having a layered structure and having no layer of rare earth element compound particles on the surface;
Lithium phosphate,
It is characterized by including.
このうち、正極活物質Ａは、単独で正極活物質として用いた場合には正極活物質の耐久性が良好であり、長期サイクル時に放電性能が低下し難いという性質を有しており、さらに、リン酸リチウムと共に混合して用いても長期サイクル時の放電性能の低下は混合しない場合と比して変化がないという性質を有している。また、正極活物質Ｂは、リン酸リチウムと共に混合して用いると正極活物質Ａの場合よりも長期サイクル時の放電性能が低下しやすくなるという性質を有している。本発明の非水電解質二次電池によれば、正極活物質として上記の正極活物質Ａ、正極活物質Ｂ及びリン酸リチウムの混合物を用いているので、正極活物質Ｂが長期サイクル時に放電性能が低下するため、連続的充電保存特性を損ねることなく、負極活物質との充放電バランスが維持され、長期サイクル特性を向上させることができるようになる。 Among these, the positive electrode active material A has a property that the durability of the positive electrode active material is good when used alone as a positive electrode active material, and the discharge performance is not easily lowered during a long-term cycle. Even when mixed with lithium phosphate, the discharge performance during long-term cycling is not changed as compared with the case of not mixing. Moreover, the positive electrode active material B has a property that when used in combination with lithium phosphate, the discharge performance during a long-term cycle is likely to be lower than that of the positive electrode active material A. According to the nonaqueous electrolyte secondary battery of the present invention, since the mixture of the positive electrode active material A, the positive electrode active material B, and lithium phosphate is used as the positive electrode active material, the positive electrode active material B has a discharge performance during a long-term cycle. Therefore, the charge / discharge balance with the negative electrode active material is maintained without impairing the continuous charge storage characteristics, and the long-term cycle characteristics can be improved.
なお、正極活物質Ａにおける希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子は、例えばリチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物粒子を分散させた溶液中で希土類元素の水酸化物を析出させ、この希土類元素の水酸化物をリチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物粒子の表面に付着させる工程と、熱処理を行う工程を含む製造方法によって得ることができる。 The fine particles comprising at least one kind of rare earth element hydroxide and oxyhydroxide in the positive electrode active material A contain, for example, lithium and cobalt, and dispersed lithium transition metal composite oxide particles having a layered structure. Depositing rare earth element hydroxide in the solution, and depositing the rare earth element hydroxide on the surface of lithium transition metal composite oxide particles containing lithium and cobalt and having a layered structure, and heat treatment It can obtain by the manufacturing method including the process of performing.
熱処理の温度としては、一般に８０〜６００℃の範囲であることが好ましく、さらに、８０〜４００℃の範囲にあることが特に好ましい。熱処理の温度が６００℃より高くなると、表面に付着した希土類元素化合物の微粒子の一部が活物質の内部に拡散し、初期の充放電効率が低下する。したがって、容量が高く、より選択的に表面に希土類元素化合物を付着した状態の活物質を得るには、熱処理温度は６００℃以下にすることが好ましい。また、水酸化物は熱処理により水酸化物、オキシ水酸化物、酸化物などの形態となるから、本発明における正極活物質表面に付着している希土類元素化合物は、水酸化物、オキシ水酸化物、酸化物などの形態で付着している。ここで、４００℃以下で熱処理した場合には、主に水酸化物や、オキシ水酸化物の状態である。熱処理時間は、３〜７時間程度であることが好ましい。 In general, the heat treatment temperature is preferably in the range of 80 to 600 ° C, and more preferably in the range of 80 to 400 ° C. When the temperature of the heat treatment is higher than 600 ° C., some of the fine particles of the rare earth element compound adhering to the surface diffuse into the active material, and the initial charge / discharge efficiency decreases. Therefore, in order to obtain an active material having a high capacity and a surface in which a rare earth element compound is adhered more selectively, the heat treatment temperature is preferably 600 ° C. or lower. Further, since the hydroxide is in the form of hydroxide, oxyhydroxide, oxide, etc. by heat treatment, the rare earth element compound adhering to the surface of the positive electrode active material in the present invention is hydroxide, oxyhydroxide. It adheres in the form of objects, oxides, etc. Here, when heat-treated at 400 ° C. or lower, it is mainly in the state of hydroxide or oxyhydroxide. The heat treatment time is preferably about 3 to 7 hours.
また、本発明における希土類元素としては、ランタン（Ｌａ）、セリウム（Ｃｅ）、プラセオジム（Ｐｒ）、ネオジム（Ｎｄ）、サマリウム（Ｓｍ）、ユーロピウム（Ｅｕ）、ガドリニウム（Ｇｄ）、テルビウム（Ｔｂ）、ジスプロシウム（Ｄｙ）、ホルミウム（Ｈｏ）、エルビウム（Ｅｒ）、ツリウム（Ｔｍ）、イッテルビウム（Ｙｂ）及びルテチウム（Ｌｕ）から選択される少なくとも１種が含まれる。なお、プロメチウム（Ｐｍ）も希土類元素の一種であるが、放射性同位元素であって安定同位体が得られないので、使用しない方がよい。より好ましい希土類元素としては、Ｅｒ、Ｓｍ、Ｎｄ、Ｙｂ、Ｔｂ、Ｄｙ、Ｈｏ、Ｔｍ、Ｌｕなどが挙げられる。 As rare earth elements in the present invention, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), At least one selected from dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu) is included. Promethium (Pm) is also a kind of rare earth element, but it is a radioisotope and a stable isotope cannot be obtained. More preferable rare earth elements include Er, Sm, Nd, Yb, Tb, Dy, Ho, Tm, and Lu.
また、本発明の非水電解質二次電池における正極として、正極活物質以外に従来から普通に使用されている導電剤や結着剤等を含んでいてもよい。また、正極の芯体としてはアルミニウム又はアルミニウム合金からなるものを用いることができる。さらに、負極活物質としては、黒鉛、コークス等の炭素材料や、酸化スズ、金属リチウム、珪素などのリチウムと合金化し得る金属及びそれらの合金等を使用することができ、負極の芯体としては銅又は銅合金からなるものを用いることができる。 In addition to the positive electrode active material, the positive electrode in the nonaqueous electrolyte secondary battery of the present invention may contain a conductive agent or a binder that has been conventionally used. Moreover, what consists of aluminum or an aluminum alloy can be used as a core of a positive electrode. Furthermore, as the negative electrode active material, carbon materials such as graphite and coke, metals that can be alloyed with lithium such as tin oxide, metallic lithium, and silicon, and alloys thereof can be used. What consists of copper or a copper alloy can be used.
また、本発明の非水電解質二次電池において使用し得る非水溶媒としては、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）などの環状炭酸エステル、フッ素化された環状炭酸エステル、γ−ブチロラクトン（ＢＬ）、γ−バレロラクトン（ＶＬ）などの環状カルボン酸エステル、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）、メチルプロピルカーボネート（ＭＰＣ）、ジブチルカーボネート（ＤＢＣ）などの鎖状炭酸エステル、フッ素化された鎖状炭酸エステル、ピバリン酸メチル、ピバリン酸エチル、メチルイソブチレート、メチルプロピオネートなどの鎖状カルボン酸エステル、Ｎ、Ｎ'−ジメチルホルムアミド、Ｎ−メチルオキサゾリジノンなどのアミド化合物、スルホランなどの硫黄化合物、テトラフルオロ硼酸１−エチル−３−メチルイミダゾリウムなどの常温溶融塩などが例示できる。これらは２種以上混合して用いることが望ましい。これらの中では、特に誘電率が大きく、非水電解液のイオン伝導度が大きい環状炭酸エステル及び鎖状炭酸エステルが好ましい。 Nonaqueous solvents that can be used in the nonaqueous electrolyte secondary battery of the present invention include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC), and fluorinated cyclic carbonates. Esters, cyclic carboxylic acid esters such as γ-butyrolactone (BL) and γ-valerolactone (VL), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), dibutyl Chain carbonates such as carbonate (DBC), fluorinated chain carbonates, chain carboxylates such as methyl pivalate, ethyl pivalate, methyl isobutyrate, methyl propionate, N, N′— Dimethylformamide, N-me Amide compounds such as oxazolidinone, sulfur compounds such as sulfolane, etc. ambient temperature molten salt such as tetrafluoroboric acid 1-ethyl-3-methylimidazolium can be exemplified. It is desirable to use a mixture of two or more of these. Among these, cyclic carbonates and chain carbonates having a particularly high dielectric constant and a high ionic conductivity of the nonaqueous electrolytic solution are preferable.
また、本発明の非水電解質二次電池で使用するセパレータとしては、ポリプロピレンやポリエチレンなどのポリオレフィン材料から形成された微多孔膜からなるセパレータが選択できる。セパレータのシャットダウン応答性を確保するために、融点の低い樹脂を混合してもよく、更には、耐熱性を得るために高融点樹脂との積層体や無機粒子を担持させた樹脂としてもよい。 In addition, as a separator used in the nonaqueous electrolyte secondary battery of the present invention, a separator made of a microporous film formed from a polyolefin material such as polypropylene or polyethylene can be selected. In order to ensure the shutdown response of the separator, a resin having a low melting point may be mixed, and further, a laminate with a high melting point resin or a resin carrying inorganic particles may be used to obtain heat resistance.
なお、本発明の非水電解質二次電池で使用する非水電解質中には、電極の安定化用化合物として、更に、ビニレンカーボネート（ＶＣ）、ビニルエチルカーボネート（ＶＥＣ）、無水コハク酸（ＳＵＣＡＨ）、無水マイレン酸（ＭＡＡＨ）、グリコール酸無水物、エチレンサルファイト（ＥＳ）、ジビニルスルホン（ＶＳ）、ビニルアセテート（ＶＡ）、ビニルピバレート（ＶＰ）、カテコールカーボネート、ビフェニル（ＢＰ）などを添加してもよい。これらの化合物は、２種以上を適宜に混合して用いることもできる。 In the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention, as a compound for stabilizing the electrode, vinylene carbonate (VC), vinyl ethyl carbonate (VEC), succinic anhydride (SUCAH) , Maleic anhydride (MAAH), glycolic anhydride, ethylene sulfite (ES), divinyl sulfone (VS), vinyl acetate (VA), vinyl pivalate (VP), catechol carbonate, biphenyl (BP), etc. Good. Two or more of these compounds can be appropriately mixed and used.
また、本発明の非水電解質二次電池で使用する非水溶媒中に溶解させる電解質塩としては、非水電解質二次電池において一般に電解質塩として用いられるリチウム塩を用いることができる。このようなリチウム塩としては、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣＦ３ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＮ（ＣＦ３ＳＯ２）（Ｃ４Ｆ９ＳＯ２）、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣ（Ｃ２Ｆ５ＳＯ２）３、ＬｉＡｓＦ６、ＬｉＣｌＯ４、Ｌｉ２Ｂ１０Ｃｌ１０、Ｌｉ２Ｂ１２Ｃｌ１２など及びそれらの混合物が例示される。これらの中でも、ＬｉＰＦ６（ヘキサフルオロリン酸リチウム）が特に好ましい。前記非水溶媒に対する電解質塩の溶解量は、０．８〜１．５ｍｏｌ／Ｌとするのが好ましい。 In addition, as the electrolyte salt dissolved in the non-aqueous solvent used in the non-aqueous electrolyte secondary battery of the present invention, a lithium salt generally used as an electrolyte salt in the non-aqueous electrolyte secondary battery can be used. Such lithium salts include 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 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 , Li 2 B 10 Cl 10 , Li 2 B 12 Cl 12 , and mixtures thereof Illustrated. Among these, LiPF 6 (lithium hexafluorophosphate) is particularly preferable. The amount of electrolyte salt dissolved in the non-aqueous solvent is preferably 0.8 to 1.5 mol / L.
更に、本発明の非水電解質二次電池においては、非水電解質は液状のものだけでなく、ゲル化されているものであってもよい。 Furthermore, in the non-aqueous electrolyte secondary battery of the present invention, the non-aqueous electrolyte may be not only liquid but also gelled.
また、本発明の非水電解質二次電池においては、前記リチウムとコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物は、一般式：ＬｉｘＣｏｙＭ１−ｙＯ２（０．９＜ｘ≦１．１、０．８≦ｙ≦１、ＭはＺｒ、Ｍｇ、Ｔｉ、Ａｌ、Ｎｉ、Ｍｎのうち少なくとも一種）で表されるものであることが好ましい。 In the nonaqueous electrolyte secondary battery of the present invention, the lithium transition metal composite oxide containing lithium and cobalt and having a layered structure is represented by the general formula: Li x Co y M 1-y O 2 (0. 9 <x ≦ 1.1, 0.8 ≦ y ≦ 1, and M is preferably represented by Zr, Mg, Ti, Al, Ni, Mn.
Ｚｒ、Ｍｇ、Ｔｉ、Ａｌ、Ｎｉ、Ｍｎのうち少なくとも一種からなるＭ成分は、高電位におけるコバルト酸リチウムの結晶構造の安定性を高め、コバルトの溶出や非水電解質の分解を抑制するように作用する。そのため、正極活物質としてこれらのＭ成分を含有するリチウムコバルト複合酸化物を用いると、正極活物質からの遷移金属イオン溶出に伴う劣化を抑制することができ、正極電位がリチウム基準で４．３Ｖを超えるまで充電しても、良好なサイクル特性と熱安定性を達成し得る非水電解質二次電池が得られるようになる。なお、このＭ成分の添加量が過小であると充分なコバルトの溶出防止効果や非水電解質の抑制効果が得らない。また、Ｍ成分の添加量が過大であると、Ｚｒ、Ｍｇ、Ｔｉ、Ａｌは電極反応に関与しないため、また、Ｎｉ、Ｍｎは初期充放電効率が低下するため、放電容量が低下してしまう。なお、正極の充電電位の上限は、高くなりすぎると正極活物質が分解するので、リチウム基準で４．６Ｖ以下とすることが好ましい。 The M component consisting of at least one of Zr, Mg, Ti, Al, Ni, and Mn enhances the stability of the lithium cobalt oxide crystal structure at a high potential, and suppresses elution of cobalt and decomposition of the nonaqueous electrolyte. Works. Therefore, when a lithium cobalt composite oxide containing these M components is used as the positive electrode active material, it is possible to suppress deterioration accompanying elution of transition metal ions from the positive electrode active material, and the positive electrode potential is 4.3 V on the basis of lithium. Even if the battery is charged to exceed, a non-aqueous electrolyte secondary battery that can achieve good cycle characteristics and thermal stability can be obtained. If the amount of M component added is too small, sufficient cobalt elution prevention effect and non-aqueous electrolyte suppression effect cannot be obtained. In addition, if the amount of M component added is excessive, Zr, Mg, Ti, and Al do not participate in the electrode reaction, and Ni and Mn decrease the initial charge / discharge efficiency, so that the discharge capacity decreases. . In addition, since the positive electrode active material is decomposed if the upper limit of the charging potential of the positive electrode becomes too high, the upper limit of the charging potential is preferably 4.6 V or less on the basis of lithium.
また、本発明の非水電解質二次電池においては、前記微粒子の平均粒子径は、１００ｎｍ以下であることが好ましい。 In the nonaqueous electrolyte secondary battery of the present invention, the average particle size of the fine particles is preferably 100 nm or less.
本発明の非水電解質二次電池においては、希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子の平均粒子径が大きくなって１００ｎｍを越えるとリチウム遷移金属複合酸化物の表面に付着し難くなって、所期の効果が奏され難くなる。また、これらの微粒子の平均粒子径が小さくなると、リチウム遷移金属複合酸化物の表面に付着し易くなるが、リチウム遷移金属複合酸化物の表面を緻密に被覆するようになるので、リチウム遷移金属複合酸化物の正極活物質としての特性が低下するようになる。より好ましい希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子の平均粒子径は、１〜１００ｎｍの範囲であり、さらに好ましくは１０〜１００ｎｍの範囲である。 In the non-aqueous electrolyte secondary battery of the present invention, when the average particle size of the fine particles comprising at least one kind of rare earth element hydroxide and oxyhydroxide becomes larger and exceeds 100 nm, the lithium transition metal composite oxide It becomes difficult to adhere to the surface of the film, and it is difficult to achieve the desired effect. In addition, when the average particle size of these fine particles becomes small, it tends to adhere to the surface of the lithium transition metal composite oxide, but since the surface of the lithium transition metal composite oxide is densely coated, the lithium transition metal composite oxide The characteristic as a positive electrode active material of an oxide comes to fall. The average particle diameter of the fine particles comprising at least one of a more preferable rare earth element hydroxide and oxyhydroxide is in the range of 1 to 100 nm, and more preferably in the range of 10 to 100 nm.
また、本発明の非水電解質二次電池においては、前記正極に占める前記正極活物質Ａと前記正極活物質Ｂとの総和に対する前記正極活物質Ａの割合は、６５質量％以上９５質量％以下であることが好ましい。 In the nonaqueous electrolyte secondary battery of the present invention, the ratio of the positive electrode active material A to the total of the positive electrode active material A and the positive electrode active material B in the positive electrode is 65% by mass or more and 95% by mass or less. It is preferable that
本発明の非水電解質二次電池においては、正極活物質Ａの割合が６５％未満であると、正極上での電解液分解反応が増加し、高温保存時のガス発生量が増加してしまう。また、正極活物質Ａの割合が９５質量％以上であると、相対的に正極活物質Ｂの割合が減るため、リン酸リチウム添加による局所的な放電性能の低下が生じ難く、高温サイクル特性が悪化する。より好ましい本発明の正極に占める正極活物質Ａと正極活物質Ｂとの総和に対する正極活物質Ａの割合は、７０〜９０質量％の範囲である。 In the nonaqueous electrolyte secondary battery of the present invention, when the proportion of the positive electrode active material A is less than 65%, the electrolytic solution decomposition reaction on the positive electrode increases, and the amount of gas generated during high-temperature storage increases. . Further, when the proportion of the positive electrode active material A is 95% by mass or more, the proportion of the positive electrode active material B is relatively reduced, so that local discharge performance is hardly deteriorated due to the addition of lithium phosphate, and the high-temperature cycle characteristics are high. Getting worse. The ratio of the positive electrode active material A to the total of the positive electrode active material A and the positive electrode active material B in the positive electrode of the present invention is more preferably in the range of 70 to 90% by mass.
また、本発明の非水電解質二次電池においては、前記正極活物質Ａにおける前記微粒子の付着量は、前記正極活物質Ａに対して０．００５質量％以上１質量％以下であることが好ましい。 In the non-aqueous electrolyte secondary battery of the present invention, the adhesion amount of the fine particles in the positive electrode active material A is preferably 0.005% by mass or more and 1% by mass or less with respect to the positive electrode active material A. .
本発明の非水電解質二次電池においては、正極活物質Ａにおける希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子の付着量が０．００５質量％未満であると、連続充電時のガス発生抑制効果を十分に得られない場合がある。また、この微粒子の付着量が１．０質量％を越えると、正極活物質の耐久性が上がるため、長期サイクル時に正負極放電性能バランスを維持することが困難になる。より好ましい微粒子の付着量は０．０１〜０．３質量％の範囲である。なお、希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子の付着量は、正極活物質Ａに対する付着量であり、例えば、微粒子の付着量が０．１質量％である場合、微粒子が付着している正極活物質Ａの１００質量部に対し、微粒子が０．１質量部付着していることを意味する。また、微粒子の付着量は希土類元素換算の値である。 In the nonaqueous electrolyte secondary battery of the present invention, the adhesion amount of fine particles comprising at least one of a rare earth element hydroxide and an oxyhydroxide in the positive electrode active material A is less than 0.005 mass%. In some cases, the effect of suppressing gas generation during continuous charging cannot be sufficiently obtained. Further, if the adhesion amount of the fine particles exceeds 1.0 mass%, the durability of the positive electrode active material increases, and it becomes difficult to maintain the positive / negative electrode discharge performance balance during a long-term cycle. A more preferable fine particle adhesion amount is in the range of 0.01 to 0.3% by mass. The adhesion amount of the fine particles composed of at least one kind of rare earth element hydroxide and oxyhydroxide is the adhesion amount to the positive electrode active material A. For example, the adhesion amount of the fine particles is 0.1% by mass. In some cases, it means that 0.1 part by mass of fine particles are attached to 100 parts by mass of the positive electrode active material A to which fine particles are attached. The amount of fine particles attached is a value in terms of rare earth elements.
また、本発明の非水電解質二次電池においては、前記正極に占める正極活物質Ａと正極活物質Ｂとリン酸リチウムの総和に対するリン酸リチウムの割合は、０．０１質量％以上１質量％以下であることが好ましい。 In the nonaqueous electrolyte secondary battery of the present invention, the ratio of lithium phosphate to the total of the positive electrode active material A, the positive electrode active material B, and lithium phosphate in the positive electrode is 0.01% by mass or more and 1% by mass. The following is preferable.
本発明の非水電解質二次電池においては、リン酸リチウムは充放電反応に寄与しないので、正極に占めるリン酸リチウムの添加量が１質量％を越えると初期充放電容量が低下してしまうために電池の高容量化が困難になり、また、０．０１質量％未満では局所的な放電性能の低下が不十分となるために高温サイクル特性が低下する。より好ましい正極に占める正極活物質Ａと正極活物質Ｂとリン酸リチウムの総和に対するリン酸リチウムの割合は、０．５質量％以下、０．０１質量％以上である。 In the nonaqueous electrolyte secondary battery of the present invention, since lithium phosphate does not contribute to the charge / discharge reaction, the initial charge / discharge capacity decreases when the amount of lithium phosphate added to the positive electrode exceeds 1% by mass. In addition, it is difficult to increase the capacity of the battery, and if it is less than 0.01% by mass, the local discharge performance is not sufficiently lowered, so that the high-temperature cycle characteristics are deteriorated. The ratio of lithium phosphate to the total of positive electrode active material A, positive electrode active material B, and lithium phosphate in the more preferable positive electrode is 0.5% by mass or less and 0.01% by mass or more.
以下、本発明を実施するための形態を実施例及び比較例を用いて詳細に説明する。ただし、以下に示す実施例は、本発明の技術思想を具体化するための非水電解質二次電池を例示するものであって、本発明をこの実施例に特定することを意図するものではなく、本発明は特許請求の範囲に示した技術思想を逸脱することなく種々の変更を行ったものにも均しく適用し得るものである。 Hereinafter, the form for implementing this invention is demonstrated in detail using an Example and a comparative example. However, the following examples illustrate non-aqueous electrolyte secondary batteries for embodying the technical idea of the present invention, and are not intended to specify the present invention to these examples. The present invention can be equally applied to various modifications without departing from the technical idea shown in the claims.
［リチウム遷移金属複合酸化物の合成］
Ｍｇ及びＡｌをそれぞれ１．５ｍｏｌ％固溶し、かつＺｒを０．０５ｍｏｌ％含有したコバルト酸リチウムを調製した。このコバルト酸リチウムは、Ｌｉ２ＣＯ３、Ｃｏ３Ｏ４、ＭｇＯ、Ａｌ２Ｏ３、ＺｒＯ２を用いて、空気雰囲気中にて、８５０℃で２４時間熱処理することにより得た。これにより得られたコバルト酸リチウムを正極活物質Ｂとして用いた。この正極活物質Ｂの表面の３万倍の走査型電子顕微鏡（ＳＥＭ）写真を図１に示した。
[Synthesis of lithium transition metal composite oxide]
Lithium cobalt oxide containing 1.5 mol% Mg and Al and 0.05 mol% Zr was prepared. This lithium cobaltate was obtained by heat treatment at 850 ° C. for 24 hours in an air atmosphere using Li 2 CO 3 , Co 3 O 4 , MgO, Al 2 O 3 , and ZrO 2 . The lithium cobaltate thus obtained was used as the positive electrode active material B. A scanning electron microscope (SEM) photograph of 30,000 times the surface of the positive electrode active material B is shown in FIG.
［正極活物質Ａ−１の合成］
上記のようにして得られたコバルト酸リチウム１０００ｇを、３リットルの純水に添加して撹拌し、コバルト酸リチウムが分散した懸濁液を調製した。この懸濁液に、硝酸エルビウム５水和物３．１８ｇを溶解した溶液を添加した。なお、硝酸エルビウム５水和物を溶解した液を懸濁液に添加する際には、１０質量％の水酸化物ナトリウム水溶液を添加し、コバルト酸リチウムを含む溶液のｐＨを９に保ちながら行った。次に、これを吸引濾過し、水洗して、得られた粉末を１２０℃で乾燥した。これにより、コバルト酸リチウムの表面に水酸化エルビウムが均一に付着したものが得られた。
[Synthesis of Positive Electrode Active Material A-1]
1000 g of lithium cobaltate obtained as described above was added to 3 liters of pure water and stirred to prepare a suspension in which lithium cobaltate was dispersed. A solution in which 3.18 g of erbium nitrate pentahydrate was dissolved was added to this suspension. In addition, when adding the liquid which melt | dissolved erbium nitrate pentahydrate to suspension, it carries out, adding 10 mass% sodium hydroxide aqueous solution, and maintaining the pH of the solution containing lithium cobaltate at 9. It was. Next, this was suction filtered, washed with water, and the obtained powder was dried at 120 ° C. Thereby, the thing which erbium hydroxide adhered uniformly to the surface of lithium cobaltate was obtained.
次に、水酸化エルビウムが付着したコバルト酸リチウムを、３００℃で５時間空気中にて熱処理し、正極活物質Ａ−１を得た。得られた正極活物質Ａ−１の３万倍のＳＥＭ写真を図２に示した。図１及び図２を対比すると明らかなように、実施例１の正極活物質Ａ−１においては、平均粒子径１００ｎｍ以下のエルビウム化合物の微粒子が、表面に均一に分散した状態で付着していることがわかる。エルビウム化合物の付着量は、エルビウム元素換算で、コバルト酸リチウムに対して、０．１２質量％であった。なお、エルビウム化合物の付着量は、ＩＣＰ（Inductivity Coupled Plasma：誘導結合プラズマ発光分析）法により測定した。 Next, lithium cobaltate to which erbium hydroxide was adhered was heat-treated in air at 300 ° C. for 5 hours to obtain a positive electrode active material A-1. An SEM photograph of 30,000 times the obtained positive electrode active material A-1 is shown in FIG. As is clear from the comparison between FIG. 1 and FIG. 2, in the positive electrode active material A-1 of Example 1, fine particles of an erbium compound having an average particle diameter of 100 nm or less adhere to the surface in a uniformly dispersed state. I understand that. The adhesion amount of the erbium compound was 0.12 mass% with respect to lithium cobaltate in terms of erbium element. In addition, the adhesion amount of the erbium compound was measured by the ICP (Inductivity Coupled Plasma) method.
［正極の作製］
上記のようにして得られた正極活物質Ａ−１と、正極活物質Ｂとを質量比で７０：３０となるように混合した後、正極活物質Ａ−１と正極活物質Ｂとリン酸リチウムの総和に対するリン酸リチウムの割合が０．３質量％となるようにリン酸リチウムを混合した。得られた正極活物質Ａ−１と正極活物質Ｂとリン酸リチウムの混合物と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを、混合物：導電剤：ポリフッ化ビニリデン＝９５：２．５：２．５（質量比）となる割合で混合し、スラリーを調製した。このスラリーをアルミ箔の両面に塗布した後乾燥し、充填密度が３．６０ｇ／ｃｍ３となるように圧延して、正極を作製した。
[Production of positive electrode]
After mixing the positive electrode active material A-1 obtained as described above and the positive electrode active material B so as to have a mass ratio of 70:30, the positive electrode active material A-1, the positive electrode active material B, and phosphoric acid Lithium phosphate was mixed so that the ratio of lithium phosphate to the total lithium was 0.3% by mass. N-methyl-2-pyrrolidone solution in which the mixture of the obtained positive electrode active material A-1, positive electrode active material B and lithium phosphate, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder were dissolved Were mixed at a ratio of mixture: conductive agent: polyvinylidene fluoride = 95: 2.5: 2.5 (mass ratio) to prepare a slurry. This slurry was applied to both sides of the aluminum foil, dried, and rolled to a packing density of 3.60 g / cm 3 to produce a positive electrode.
［負極の作製］
負極は、炭素材（黒鉛）と、ＣＭＣ（カルボキシメチルセルロースナトリウム）と、ＳＢＲ（スチレンブタジエンゴム）とを、９８：１：１の質量比となるように水溶液中で混合し、スラリーを調製した。このスラリーを、銅箔の両面に塗布した後、乾燥し圧延して負極を作製した。なお、負極活物質の充填密度は１．７ｇ／ｃｍ３であった。
[Production of negative electrode]
The negative electrode was prepared by mixing a carbon material (graphite), CMC (carboxymethyl cellulose sodium), and SBR (styrene butadiene rubber) in an aqueous solution so as to have a mass ratio of 98: 1: 1. After apply | coating this slurry to both surfaces of copper foil, it dried and rolled and produced the negative electrode. The packing density of the negative electrode active material was 1.7 g / cm 3 .
［電解液の作製］
エチレンカーボネート（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）とジエチルカーボネート（ＤＥＣ）とを体積比３：６：１で混合した溶媒に対し、ヘキサフルオロリン酸リチウム（ＬｉＰＦ６）を、濃度が１ｍｏｌ／Ｌとなるように溶解して、電解液を作製した。
[Preparation of electrolyte]
Lithium hexafluorophosphate (LiPF 6 ) was added at a concentration of 1 mol / L to a solvent in which ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed at a volume ratio of 3: 6: 1. It melt | dissolved so that it might become, and produced electrolyte solution.
［電池の作製］
このようにして得た正極および負極を、セパレーターを介して対向するように巻取って巻取り体を作製し、Ａｒ雰囲気下のグローブボックス中にて、巻取り体を電解液ともにアルミニウムラミネートに封入することにより、電池規格サイズとして、厚み３．６ｍｍ×幅３５ｍｍ×長さ６２ｍｍの、実施例１にかかる非水電解質二次電池を作製した。
[Production of battery]
The positive electrode and the negative electrode thus obtained are wound so as to face each other through a separator, and a wound body is produced. The wound body is enclosed in an aluminum laminate together with an electrolyte in a glove box under an Ar atmosphere. Thus, a nonaqueous electrolyte secondary battery according to Example 1 having a thickness of 3.6 mm, a width of 35 mm, and a length of 62 mm was produced as a standard battery size.
硝酸エルビウム５水和物に代えて、硝酸サマリウム６水和物３．５４ｇを用いた以外は、実施例１と同様にして正極活物質Ａ−２を作製した。得られた正極活物質Ａ−２についてＳＥＭで観察したところ、平均粒子径１００ｎｍ以下のサマリウム化合物が表面に均一に付着していた。サマリウム化合物の付着量は、サマリウム元素換算で、コバルト酸リチウムに対して、０．１２質量％であった。そして、正極活物質Ａ−１に代えて正極活物質Ａ−２を用いたこと以外は、上記実施例１の場合と同様にして実施例２にかかる非水電解質二次電池を作製した。 A positive electrode active material A-2 was produced in the same manner as in Example 1 except that 3.54 g of samarium nitrate hexahydrate was used instead of erbium nitrate pentahydrate. When the obtained positive electrode active material A-2 was observed by SEM, a samarium compound having an average particle diameter of 100 nm or less was uniformly attached to the surface. The adhesion amount of the samarium compound was 0.12% by mass with respect to lithium cobaltate in terms of samarium element. And the nonaqueous electrolyte secondary battery concerning Example 2 was produced like the case of the said Example 1 except having replaced with positive electrode active material A-1 and having used positive electrode active material A-2.
硝酸エルビウム５水和物に代えて、硝酸ネオジム６水和物３．６５ｇを用いた以外は、実施例１と同様にして正極活物質Ａ−３を作製した。得られた正極活物質Ａ−３についてＳＥＭで観察したところ、平均粒子径１００ｎｍ以下のネオジム化合物が表面に均一に付着していた。ネオジム化合物の付着量は、ネオジム元素換算で、コバルト酸リチウムに対して、０．１２質量％であった。そして、正極活物質Ａ−１に代えて正極活物質Ａ−３を用いたこと以外は、上記実施例１と同様にして実施例３にかかる非水電解質二次電池を作製した。 A positive electrode active material A-3 was produced in the same manner as in Example 1 except that 3.65 g of neodymium nitrate hexahydrate was used instead of erbium nitrate pentahydrate. When the obtained positive electrode active material A-3 was observed by SEM, a neodymium compound having an average particle diameter of 100 nm or less was uniformly attached to the surface. The adhesion amount of the neodymium compound was 0.12% by mass with respect to lithium cobaltate in terms of neodymium element. And the nonaqueous electrolyte secondary battery concerning Example 3 was produced like the said Example 1 except having replaced with positive electrode active material A-1 and having used positive electrode active material A-3.
コバルト酸リチウムを分散させた懸濁液に、硝酸エルビウム５水和物１３．２５ｇを溶解した溶液を添加した以外は、実施例１と同様にして正極活物質Ａ−４を作製した。得られた正極活物質Ａ−４についてＳＥＭで観察したところ、平均粒子径１００ｎｍ以下のエルビウム化合物が表面に均一に付着していた。エルビウム化合物の付着量は、エルビウム元素換算で、コバルト酸リチウムに対して、０．５質量％であった。そして、正極活物質Ａ−１に代えて正極活物質Ａ−４を用いたこと以外は、上記実施例１と同様にして実施例４にかかる非水電解質二次電池を作製した。 A positive electrode active material A-4 was produced in the same manner as in Example 1 except that a solution in which 13.25 g of erbium nitrate pentahydrate was dissolved was added to the suspension in which lithium cobaltate was dispersed. When the obtained positive electrode active material A-4 was observed with an SEM, an erbium compound having an average particle diameter of 100 nm or less was uniformly attached to the surface. The adhesion amount of the erbium compound was 0.5 mass% with respect to lithium cobaltate in terms of erbium element. And the nonaqueous electrolyte secondary battery concerning Example 4 was produced like the said Example 1 except having replaced with positive electrode active material A-1 and having used positive electrode active material A-4.
上記のようにして得られた正極活物質Ａ−１と、正極活物質Ｂとを質量比で９５：５となるように混合したこと以外は、上記実施例１と同様にして実施例５にかかる非水電解質二次電池を作製した。 Example 5 was performed in the same manner as in Example 1 except that the positive electrode active material A-1 obtained as described above and the positive electrode active material B were mixed at a mass ratio of 95: 5. Such a non-aqueous electrolyte secondary battery was produced.
［比較例１］
上記正極活物質Ａ−１及びリン酸リチウムを含まず、上述のようにして得られた正極活物質Ｂと、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを混合したこと以外は、上記実施例１と同様にして比較例１にかかる非水電解質二次電池を作製した。
[Comparative Example 1]
N in which the positive electrode active material B and the positive electrode active material B obtained as described above, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder are dissolved without including the positive electrode active material A-1 and lithium phosphate. A nonaqueous electrolyte secondary battery according to Comparative Example 1 was produced in the same manner as in Example 1 except that the -methyl-2-pyrrolidone solution was mixed.
［比較例２］
正極活物質Ａ−１を含まず、上述のようにして得られた正極活物質Ｂとリン酸リチウムの総和に対するリン酸リチウムの割合が０．３質量％となるようにリン酸リチウムを混合した。得られた正極活物質Ｂとリン酸リチウムの混合物と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを混合したこと以外は、上記実施例１と同様にして比較例２にかかる非水電解質二次電池を作製した。
[Comparative Example 2]
Lithium phosphate was mixed so that the ratio of lithium phosphate to the total of positive electrode active material B and lithium phosphate obtained as described above was 0.3% by mass, not including positive electrode active material A-1. . Except for the mixture of the obtained positive electrode active material B and lithium phosphate, acetylene black as a conductive agent, and N-methyl-2-pyrrolidone solution in which polyvinylidene fluoride as a binder was dissolved A nonaqueous electrolyte secondary battery according to Comparative Example 2 was produced in the same manner as in Example 1 above.
［比較例３］
正極活物質Ｂ及びリン酸リチウムを含まず、上述のようにして得られた正極活物質Ａ−１と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを混合したこと以外は、上記実施例１と同様にして比較例３にかかる非水電解質二次電池を作製した。
[Comparative Example 3]
N- not containing positive electrode active material B and lithium phosphate, and obtained by dissolving positive electrode active material A-1 obtained as described above, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder. A nonaqueous electrolyte secondary battery according to Comparative Example 3 was produced in the same manner as in Example 1 except that the methyl-2-pyrrolidone solution was mixed.
［比較例４］
上記のようにして得られた正極活物質Ａ−１と、正極活物質Ｂとを質量比で７０：３０となるように混合した。そして、リン酸リチウムを含まず、得られた正極活物質Ａと正極活物質Ｂとの混合物と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを混合したこと以外は、上記実施例１と同様にして比較例４にかかる非水電解質二次電池を作製した。
[Comparative Example 4]
The positive electrode active material A-1 obtained as described above and the positive electrode active material B were mixed at a mass ratio of 70:30. And N-methyl- which did not contain lithium phosphate, dissolved the mixture of the obtained positive electrode active material A and positive electrode active material B, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder. A nonaqueous electrolyte secondary battery according to Comparative Example 4 was produced in the same manner as in Example 1 except that the 2-pyrrolidone solution was mixed.
［比較例５］
正極活物質Ｂを含まず、上記のようにして得られた正極活物質Ａ−１とリン酸リチウムの総和に対するリン酸リチウムの割合が０．３質量％となるようにリン酸リチウムを混合した。得られた正極活物質Ａ−１とリン酸リチウムの混合物と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンを溶解させたＮ−メチル−２−ピロリドン溶液とを混合したこと以外は、上記実施例１と同様にして比較例５にかかる非水電解質二次電池を作製した。
[Comparative Example 5]
Lithium phosphate was mixed so that the ratio of lithium phosphate with respect to the total of positive electrode active material A-1 obtained as described above and lithium phosphate was 0.3% by mass without including positive electrode active material B. . Mixing the obtained positive electrode active material A-1 and lithium phosphate mixture, acetylene black as a conductive agent, and N-methyl-2-pyrrolidone solution in which polyvinylidene fluoride as a binder was dissolved A nonaqueous electrolyte secondary battery according to Comparative Example 5 was produced in the same manner as Example 1 except for the above.
［比較例６］
実施例１の正極活物質の作製において、酸化エルビウムをコバルト酸リチウムの原料に添加し、エルビウムが０．１２質量％内部に固溶した正極活物質Ａ−６を作製した。正極活物質Ａ−１に代えて正極活物質Ａ−６を用いたこと以外は、上記実施例１と同様にして比較例６にかかる非水電解質二次電池を作製した。
[Comparative Example 6]
In preparation of the positive electrode active material of Example 1, erbium oxide was added to the raw material of lithium cobaltate, and positive electrode active material A-6 in which erbium was dissolved in 0.12% by mass was prepared. A nonaqueous electrolyte secondary battery according to Comparative Example 6 was produced in the same manner as in Example 1 except that the positive electrode active material A-6 was used instead of the positive electrode active material A-1.
［比較例７］
実施例１の正極活物質の作製において得られたコバルト酸リチウム１ｋｇに対して１．３７ｇの酸化エルビウムを添加し、らいかい機で混合し、酸化エルビウムが混合された正極活物質Ａ−７を得た。この比較例７において作製された正極活物質Ａ−７の表面の３万倍のＳＥＭ写真を図３に示した。なお、図３の中心部に位置する粒子は、酸化エルビウムの粒子であり、粒子径３００〜４００ｎｍの粒子である。図３に示すように、比較例７の正極活物質Ａ−７においては、その表面に酸化エルビウムの微粒子は、コバルト酸リチウムと混合状態にあるが、コバルト酸リチウムの表面には付着しておらず、コバルト酸リチウムの表面において偏在していることが確認された。そして、正極活物質Ａ−１に代えて正極活物質Ａ−７を用いたこと以外は、上記実施例１と同様にして比較例７にかかる非水電解質二次電池を作製した。
[Comparative Example 7]
1.37 g of erbium oxide was added to 1 kg of lithium cobaltate obtained in the preparation of the positive electrode active material of Example 1, and the mixture was mixed with a cracking machine to obtain a positive electrode active material A-7 mixed with erbium oxide. Obtained. A SEM photograph of 30,000 times the surface of the positive electrode active material A-7 produced in Comparative Example 7 is shown in FIG. In addition, the particle | grains located in the center part of FIG. 3 are erbium oxide particles, and are particles having a particle diameter of 300 to 400 nm. As shown in FIG. 3, in the positive electrode active material A-7 of Comparative Example 7, erbium oxide fine particles are mixed with lithium cobalt oxide on the surface thereof, but are not attached to the surface of lithium cobalt oxide. It was confirmed that it was unevenly distributed on the surface of lithium cobaltate. And the nonaqueous electrolyte secondary battery concerning the comparative example 7 was produced like the said Example 1 except having replaced with positive electrode active material A-1 and having used positive electrode active material A-7.
［比較例８］
硝酸エルビウム５水和物に代えて、ジルコニウムオキシナイトレート２水和物を３．５１ｇ用いたこと以外は実施例１と同様にして、正極活物質Ａ−８を作製した。この正極活物質Ａ−８は、表面にＺｒ化合物が付着した正極活物質である。ＳＥＭにて観察した結果、実施例１の正極活物質と同様に、正極活物質の表面に平均粒子径１００ｎｍ以下のジルコニウム化合物が均一に付着していた。正極活物質Ａ−１に代えて正極活物質Ａ−８を用いたこと以外は、上記実施例１と同様にして比較例８にかかる非水電解質二次電池を作製した。
[Comparative Example 8]
A positive electrode active material A-8 was produced in the same manner as in Example 1 except that 3.51 g of zirconium oxynitrate dihydrate was used instead of erbium nitrate pentahydrate. This positive electrode active material A-8 is a positive electrode active material having a Zr compound attached to the surface. As a result of observation by SEM, as with the positive electrode active material of Example 1, a zirconium compound having an average particle diameter of 100 nm or less was uniformly attached to the surface of the positive electrode active material. A nonaqueous electrolyte secondary battery according to Comparative Example 8 was produced in the same manner as in Example 1 except that the positive electrode active material A-8 was used instead of the positive electrode active material A-1.
［電池の評価］
上記のようにして作成された実施例１〜５及び比較例１〜８の各電池について、下記の条件で高温サイクル特性試験及び高温連続充電保存試験を行った。この結果を下記表１に示す。
[Battery evaluation]
About each battery of Examples 1-5 and Comparative Examples 1-8 produced as mentioned above, the high temperature cycling characteristic test and the high temperature continuous charge storage test were done on condition of the following. The results are shown in Table 1 below.
［高温サイクル特性試験］
・充電：１Ｉｔ（７５０ｍＡ）の電流で電池電圧が４．４Ｖとなるまで定電流充電を行い、その後４．４Ｖの定電圧で電流３７．５ｍＡになるまで充電した。このときの正極電位は、リチウム基準で４．５Ｖである。
・放電：１Ｉｔ（７５０ｍＡ）の電流で電池電圧が２．７５Ｖとなるまで定電流放電を行った。
・休止：充電と放電の間の休止間隔は、１０分間とした。
・環境温度：サイクル試験は４５℃の恒温槽内で実施した。
上記の充放電条件で充放電サイクルを繰り返し、５００サイクル目の放電容量を求め、以下の計算式によってサイクル特性（％）を求めた。
サイクル特性（％）
＝（５００サイクル目放電容量／１サイクル目放電容量）×１００
[High-temperature cycle characteristics test]
-Charging: Constant current charging was performed at a current of 1 It (750 mA) until the battery voltage reached 4.4 V, and then charging was performed at a constant voltage of 4.4 V until the current reached 37.5 mA. The positive electrode potential at this time is 4.5 V on the basis of lithium.
Discharge: Constant current discharge was performed at a current of 1 It (750 mA) until the battery voltage reached 2.75V.
-Pause: The pause interval between charging and discharging was 10 minutes.
-Environmental temperature: The cycle test was conducted in a constant temperature bath at 45 ° C.
The charge / discharge cycle was repeated under the above charge / discharge conditions, the discharge capacity at the 500th cycle was determined, and the cycle characteristics (%) were determined by the following formula.
Cycle characteristics (%)
= (500th cycle discharge capacity / 1st cycle discharge capacity) × 100
［６０℃連続充電試験］
連続充電前の電池厚みを測定し、上記の充放電条件で、連続充電試験前の放電容量（Ｑ０）を室温（２５℃）にて測定した。測定後の電池を６０℃の恒温槽に一時間放置した後、６０℃の環境のまま、７５０ｍＡの定電流で電池電圧が４．４Ｖになるまで充電し、さらに４．４Ｖの定電圧で、充電のトータル時間が８０時間となるまで連続充電を行った。連続充電後の電池厚みを測定し、連続充電前の電池厚みを差し引くことで電池膨れ（ｍｍ）を求めた。その後、室温まで冷却して、室温にて、７５０ｍＡの定電流で電池電圧が２．７５Ｖになるまで放電して、連続充電試験後の放電容量（Ｑ１）を測定し、以下の式から、残存容量率（％）を求めた。
残存容量率（％）
＝［連続充電試験後の放電容量（Ｑ１）／連続充電試験前の放電容量（Ｑ０）］
×１００
[60 ° C continuous charge test]
The battery thickness before continuous charge was measured, and the discharge capacity (Q0) before the continuous charge test was measured at room temperature (25 ° C.) under the above charge / discharge conditions. The battery after measurement was left in a constant temperature bath at 60 ° C. for 1 hour, and then charged with a constant current of 750 mA until the battery voltage reached 4.4 V while maintaining the environment at 60 ° C., and at a constant voltage of 4.4 V, Continuous charging was performed until the total charging time reached 80 hours. The battery thickness after continuous charging was measured, and the battery swelling (mm) was determined by subtracting the battery thickness before continuous charging. Thereafter, the battery was cooled to room temperature, discharged at room temperature at a constant current of 750 mA until the battery voltage reached 2.75 V, and the discharge capacity (Q1) after the continuous charge test was measured. The capacity rate (%) was determined.
Remaining capacity ratio (%)
= [Discharge capacity after continuous charge test (Q1) / Discharge capacity before continuous charge test (Q0)]
× 100
表１に示した結果から以下のことが分かる。すなわち、本発明に従う実施例１〜５の電池は、比較例１〜８の電池に比べて、高いサイクル容量維持率を示し、また表面に希土類元素化合物の微粒子が被覆されていない比較例１及び２や、エルビウムを固溶させた比較例６、酸化エルビウムを添加した比較例７、ジルコニウム化合物で被覆した比較例８に比べて、連続充電保存時の電池膨れも抑制されている。 From the results shown in Table 1, the following can be understood. That is, the batteries of Examples 1 to 5 according to the present invention show a higher cycle capacity maintenance ratio than the batteries of Comparative Examples 1 to 8, and Comparative Example 1 in which the surface is not coated with fine particles of rare earth element compounds. 2 and Comparative Example 6 in which erbium is dissolved, Comparative Example 7 in which erbium oxide is added, and Comparative Example 8 in which the compound is coated with a zirconium compound, swelling of the battery during continuous charge storage is also suppressed.
また、比較例１、２においては、正極活物質表面に希土類元素化合物が付着した正極活物質Ａを含まないため、高温・高電圧下での電解液分解が促進され、高温サイクル特性や保存特性が悪化している。さらに、比較例３においては、正極活物質表面に希土類元素化合物が付着した正極活物質Ａのみを単独で用いたため、正極活物質の耐久性が高く、長期サイクル時に放電性能が低下し難くなるため、相対的に負極活物質の放電性能の低下が大きくなることで正負極間の充放電性能バランスが崩れ、高温サイクル時の容量維持率が低下している。 Moreover, in Comparative Examples 1 and 2, since the positive electrode active material A having a rare earth element compound attached to the surface of the positive electrode active material is not included, decomposition of the electrolyte solution under high temperature and high voltage is promoted, and high temperature cycle characteristics and storage characteristics. Is getting worse. Furthermore, in Comparative Example 3, since only the positive electrode active material A having the rare earth element compound adhered to the surface of the positive electrode active material is used alone, the positive electrode active material has high durability, and the discharge performance is unlikely to deteriorate during a long-term cycle. However, since the decrease in the discharge performance of the negative electrode active material is relatively large, the balance between the charge and discharge performance between the positive and negative electrodes is lost, and the capacity retention rate during the high-temperature cycle is reduced.
なお、比較例４に示す、正極活物質Ａと正極活物質Ｂとを混合しただけの場合や、比較例５に示す正極活物質Ａとリン酸リチウムのみを混合した場合では、高温サイクル特性の改善効果は僅かであった。そのため、本実施例１〜５に示すような組合せにて初めてその効果を発揮することが確認できた。このような結果が得られることの詳細は明確ではないが、正極活物質に添加したリン酸リチウムは、充放電サイクルを繰り返す中で正極表面に希土類元素化合物が付着していない正極活物質Ｂに選択的に作用し、局所的に正極の放電性能（レート特性）を低下させるため、負極との充放電性能バランスが維持され、高温サイクル特性が改善すると考えられる。 In addition, when only the positive electrode active material A and the positive electrode active material B shown in Comparative Example 4 are mixed, or when only the positive electrode active material A and lithium phosphate shown in Comparative Example 5 are mixed, the high temperature cycle characteristics The improvement effect was slight. Therefore, it was confirmed that the effects were exhibited for the first time in the combinations as shown in Examples 1 to 5. Although the details that such a result is obtained are not clear, the lithium phosphate added to the positive electrode active material is added to the positive electrode active material B in which the rare earth element compound is not attached to the positive electrode surface during repeated charge and discharge cycles. Since it acts selectively and locally lowers the discharge performance (rate characteristics) of the positive electrode, it is considered that the charge / discharge performance balance with the negative electrode is maintained and the high-temperature cycle characteristics are improved.
比較例６においては、希土類元素が正極活物質の表面では無く、内部に固溶しているため、電解液の分解反応抑制が不十分であり、実施例１に比べて高温サイクルや連続充電保存特性が悪化している。また、比較例７においては、希土類元素化合物が正極活物質の表面に均一に分散しておらず、正極活物質表面の一部に酸化エルビウムが偏在しているため、電解液の反応抑制が不十分であり、実施例１に比べて高温サイクルや連続充電保存特性が悪化している。 In Comparative Example 6, since the rare earth element is not dissolved on the surface of the positive electrode active material but is dissolved in the inside, the decomposition reaction of the electrolytic solution is not sufficiently suppressed. The characteristics are getting worse. Further, in Comparative Example 7, the rare earth element compound is not uniformly dispersed on the surface of the positive electrode active material, and erbium oxide is unevenly distributed on a part of the surface of the positive electrode active material. This is sufficient, and the high-temperature cycle and continuous charge storage characteristics are deteriorated as compared with Example 1.
さらに、比較例８においては、正極活物質表面にジルコニウム化合物が付着しているが、ジルコニウム化合物は希土類元素化合物に比べて電解液の分解反応を抑制する効果が小さいため、実施例１〜５に比べて、高温サイクル特性は連続充電保存特性が悪化している。また実施例４に比べて希土類元素化合物の被覆量を減らした実施例１は、正極活物質の耐久性を下げることができるため高温サイクル時の正負極放電性能バランスを維持しやすく、更にサイクル特性が向上している。また実施例５に比べて正極活物質Ｂの混合量を増やした実施例１は、リン酸リチウムが局所的に作用する範囲が増えるため、更にサイクル特性が向上する。 Furthermore, in Comparative Example 8, the zirconium compound is adhered to the surface of the positive electrode active material. However, since the zirconium compound has a smaller effect of suppressing the decomposition reaction of the electrolytic solution than the rare earth element compound, Examples 1 to 5 are used. Compared with the high-temperature cycle characteristics, the continuous charge storage characteristics are deteriorated. Further, in Example 1 in which the coating amount of the rare earth element compound is reduced as compared with Example 4, the durability of the positive electrode active material can be lowered, so that it is easy to maintain the positive / negative electrode discharge performance balance during the high temperature cycle, and further the cycle characteristics. Has improved. Further, in Example 1 in which the mixing amount of the positive electrode active material B is increased as compared with Example 5, the range in which lithium phosphate acts locally increases, so that the cycle characteristics are further improved.
以上述べたように、本発明の非水電解質二次電池によれば、正極活物質として、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子が付着している正極活物質Ａと、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の化合物の微粒子が付着していない正極活物質Ｂと、
リン酸リチウム（Ｌｉ３ＰＯ４）と、
を含むものを用いることにより、連続充電保存特性を損ねることなく、負極活物質との充放電バランスを維持し、長期サイクル特性を向上させることが可能となることが確認された。
As described above, according to the nonaqueous electrolyte secondary battery of the present invention, as the positive electrode active material,
A lithium transition metal composite oxide containing lithium and cobalt and having a layered structure, the surface of which is coated with fine particles of at least one of a rare earth hydroxide and an oxyhydroxide Substance A;
A positive electrode active material B containing lithium and cobalt and having a layered structure and having no layer of rare earth element compound particles on the surface;
Lithium phosphate (Li 3 PO 4 );
It has been confirmed that the use of a material containing, can maintain the charge / discharge balance with the negative electrode active material and improve the long-term cycle characteristics without impairing the continuous charge storage characteristics.
なお、上記実施例１〜５では、希土類元素としてＥｒ、Ｓｍ及びＮｄを用いた例のみ示したが、希土類元素は類似の化学的ないし物理的特性を備えていることが周知であるので、その他の希土類元素、すなわち、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｔｍ、Ｙｂ及びＬｕも同様に用いることができる。更に、これらの希土類元素は、単独の場合だけでなく、適宜複数種混合して用いることができる。 In Examples 1 to 5, only examples using Er, Sm, and Nd as the rare earth elements are shown, but it is well known that the rare earth elements have similar chemical or physical characteristics. These rare earth elements, namely, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu can be used in the same manner. Furthermore, these rare earth elements can be used not only in the case of individual but also in a mixture of plural kinds as appropriate.
Claims (6)
前記正極は、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の水酸化物及びオキシ水酸化物のうちの少なくとも１種からなる微粒子が付着している正極活物質Ａと、
リチウム及びコバルトを含有し、層状構造を有するリチウム遷移金属複合酸化物であって、表面に希土類元素の化合物の微粒子が付着していない正極活物質Ｂと、
リン酸リチウムと、
を含んでいることを特徴とする非水電解質二次電池。 In a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a separator, and a nonaqueous electrolyte,
The positive electrode is
A lithium transition metal composite oxide containing lithium and cobalt and having a layered structure, the surface of which is coated with fine particles of at least one of a rare earth hydroxide and an oxyhydroxide Substance A;
A positive electrode active material B containing lithium and cobalt and having a layered structure and having no layer of rare earth element compound particles on the surface;
Lithium phosphate,
A non-aqueous electrolyte secondary battery comprising:
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| WO2014049958A1 (en) * | 2012-09-28 | 2014-04-03 | 三洋電機株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery using said positive electrode active material |
| WO2014068831A1 (en) * | 2012-10-31 | 2014-05-08 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
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