JP4707313B2 - Non-aqueous solvent type secondary battery - Google Patents
Non-aqueous solvent type secondary battery Download PDFInfo
- Publication number
- JP4707313B2 JP4707313B2 JP2003326733A JP2003326733A JP4707313B2 JP 4707313 B2 JP4707313 B2 JP 4707313B2 JP 2003326733 A JP2003326733 A JP 2003326733A JP 2003326733 A JP2003326733 A JP 2003326733A JP 4707313 B2 JP4707313 B2 JP 4707313B2
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- electrolyte
- aqueous solvent
- mass
- succinimide
- 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.)
- Expired - Lifetime
Links
- 239000003125 aqueous solvent Substances 0.000 title claims description 75
- -1 cyclic acid anhydride Chemical class 0.000 claims description 105
- 239000003792 electrolyte Substances 0.000 claims description 64
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 55
- 229960002317 succinimide Drugs 0.000 claims description 53
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 12
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- 229940014800 succinic anhydride Drugs 0.000 claims description 7
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethylsuccinimide Chemical compound CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- KYEACNNYFNZCST-UHFFFAOYSA-N 1-methylpyrrolidine-2,5-dione Chemical compound CN1C(=O)CCC1=O KYEACNNYFNZCST-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- PENBMGNNJROBRG-UHFFFAOYSA-N 1-(2-methylpropyl)pyrrolidine-2,5-dione Chemical compound CC(C)CN1C(=O)CCC1=O PENBMGNNJROBRG-UHFFFAOYSA-N 0.000 claims description 2
- JHULURRVRLTSRD-UHFFFAOYSA-N 1-cyclohexylpyrrolidine-2,5-dione Chemical compound O=C1CCC(=O)N1C1CCCCC1 JHULURRVRLTSRD-UHFFFAOYSA-N 0.000 claims description 2
- VOCDJQSAMZARGX-UHFFFAOYSA-N 1-ethenylpyrrolidine-2,5-dione Chemical compound C=CN1C(=O)CCC1=O VOCDJQSAMZARGX-UHFFFAOYSA-N 0.000 claims description 2
- ZTUKZULGOCFJET-UHFFFAOYSA-N 1-phenylpyrrolidine-2,5-dione Chemical compound O=C1CCC(=O)N1C1=CC=CC=C1 ZTUKZULGOCFJET-UHFFFAOYSA-N 0.000 claims description 2
- AXEUBXNTRJZUKG-UHFFFAOYSA-N 1-prop-2-enylpyrrolidine-2,5-dione Chemical compound C=CCN1C(=O)CCC1=O AXEUBXNTRJZUKG-UHFFFAOYSA-N 0.000 claims description 2
- ZYRNGRIPNYDMCV-UHFFFAOYSA-N 1-propan-2-ylpyrrolidine-2,5-dione Chemical compound CC(C)N1C(=O)CCC1=O ZYRNGRIPNYDMCV-UHFFFAOYSA-N 0.000 claims description 2
- ACJPFLIEHGFXGP-UHFFFAOYSA-N 3,3-dimethyloxolane-2,5-dione Chemical compound CC1(C)CC(=O)OC1=O ACJPFLIEHGFXGP-UHFFFAOYSA-N 0.000 claims description 2
- FGQUIQAGZLBOGL-UHFFFAOYSA-N 3-non-1-enyloxolane-2,5-dione Chemical compound CCCCCCCC=CC1CC(=O)OC1=O FGQUIQAGZLBOGL-UHFFFAOYSA-N 0.000 claims description 2
- NVPRNSAYSSEIGR-UHFFFAOYSA-N 3-phenyloxane-2,6-dione Chemical compound O=C1OC(=O)CCC1C1=CC=CC=C1 NVPRNSAYSSEIGR-UHFFFAOYSA-N 0.000 claims description 2
- HDFKMLFDDYWABF-UHFFFAOYSA-N 3-phenyloxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1=CC=CC=C1 HDFKMLFDDYWABF-UHFFFAOYSA-N 0.000 claims description 2
- HFUKQDYIECVXLI-UHFFFAOYSA-N CCC(C)(C)N1C(=O)CCC1=O Chemical compound CCC(C)(C)N1C(=O)CCC1=O HFUKQDYIECVXLI-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- FNZBSNUICNVAAM-UHFFFAOYSA-N trimethyl-[methyl-[methyl-(methyl-phenyl-trimethylsilyloxysilyl)oxy-phenylsilyl]oxy-phenylsilyl]oxysilane Chemical compound C=1C=CC=CC=1[Si](C)(O[Si](C)(C)C)O[Si](C)(C=1C=CC=CC=1)O[Si](C)(O[Si](C)(C)C)C1=CC=CC=C1 FNZBSNUICNVAAM-UHFFFAOYSA-N 0.000 claims description 2
- DFATXMYLKPCSCX-UHFFFAOYSA-N 3-methylsuccinic anhydride Chemical compound CC1CC(=O)OC1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 28
- 238000003860 storage Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 17
- 230000002829 reductive effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- 239000011149 active material Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000011245 gel electrolyte Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000004292 cyclic ethers Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013733 LiCo 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BURFSVXOAOTJIC-UHFFFAOYSA-N O1CCC1.O1CCC1.C(COCCOCCOCCO)O Chemical compound O1CCC1.O1CCC1.C(COCCOCCOCCO)O BURFSVXOAOTJIC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Description
本発明は、非水溶媒系二次電池に関し、更に詳しくは、初回放電容量が大きく、高負荷放電効率及び高温充電保存特性に優れた非水溶媒系二次電池に関する。 The present invention relates to a non-aqueous solvent secondary battery, and more particularly to a non-aqueous solvent secondary battery having a large initial discharge capacity and excellent high-load discharge efficiency and high-temperature charge storage characteristics.
携帯型の電子機器の急速な普及に伴い、それに使用される電池への要求仕様は、年々厳しくなり、特に小型・薄型化、高容量でサイクル特性が優れ、性能の安定したものが要求されている。そして、二次電池分野では他の電池に比べて高エネルギー密度であるリチウム非水溶媒系二次電池が注目され、このリチウム非水溶媒系二次電池の占める割合は二次電池市場において大きな伸びを示している。 With the rapid spread of portable electronic devices, the required specifications for the batteries used for them are becoming stricter year by year, and in particular, small and thin, high capacity, excellent cycle characteristics, and stable performance are required. Yes. In the field of secondary batteries, lithium non-aqueous solvent secondary batteries, which have a higher energy density than other batteries, are attracting attention. The proportion of lithium non-aqueous solvent secondary batteries accounts for a significant increase in the secondary battery market. Is shown.
このリチウム非水溶媒系二次電池は、細長いシート状の銅箔等からなる負極芯体（集電体）の両面に負極用活物質合剤を被膜状に塗布した負極と、細長いシート状のアルミニウム箔等からなる正極芯体の両面に正極用活物質合剤を被膜状に塗布した正極との間に、微多孔性ポリプロピレンフィルム等からなるセパレータを配置し、負極及び正極をセパレータにより互いに絶縁した状態で円柱状又は楕円形状に巻回した後、角型電池の場合は更に巻回電極体を押し潰して偏平状に形成し、負極及び正極の各所定部分にそれぞれ負極リード及び正極リードを接続して所定形状の外装内に収納した構成を有している。 This lithium non-aqueous solvent type secondary battery includes a negative electrode in which a negative electrode active material mixture is applied in a film form on both sides of a negative electrode core (current collector) made of an elongated sheet-like copper foil and the like, and an elongated sheet-like battery A separator made of a microporous polypropylene film or the like is placed between both sides of a positive electrode core made of aluminum foil or the like and coated with a positive electrode active material mixture in the form of a film, and the negative electrode and the positive electrode are insulated from each other by the separator. In the case of a rectangular battery, the wound electrode body is further crushed to form a flat shape, and a negative electrode lead and a positive electrode lead are respectively attached to predetermined portions of the negative electrode and the positive electrode. It has the structure which connected and accommodated in the exterior of a predetermined shape.
このような非水溶媒系二次電池に使用される非水溶媒には、電解質を電離させるために誘電率が高い必要があること、及び、広い温度範囲でイオン伝導度が高い必要があるということから、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）、ジエチルカーボネート（ＤＥＣ）等のカーボネート類、γ−ブチロラクトン等のラクトン類、その他、エーテル類、ケトン類、エステル類などの有機溶媒が使用されており、特にＥＣと粘度の低い非環状炭酸エステル、例えば、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、メチルエチルカーボネート（ＭＥＣ）等の混合溶媒が広く使用されているが、蒸気圧が低いために高温放置すると電池が膨れやすいという問題点を有していた。 The non-aqueous solvent used in such a non-aqueous solvent type secondary battery needs to have a high dielectric constant in order to ionize the electrolyte, and needs to have high ionic conductivity in a wide temperature range. Therefore, carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), diethyl carbonate (DEC), lactones such as γ-butyrolactone, etc., ethers, ketones, esters, etc. Organic solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC) are widely used. However, due to the low vapor pressure, the battery tends to swell when left at high temperatures. It had.
一方、ＰＣないしはＢＣを含有する非水溶媒は、蒸気圧が高く、また酸化電位も高くなるために分解し難くなるのでガスの発生量が少なく、電池が膨れ難いという優れた効果を奏すると共に、凝固点が低いために低温特性も優れているという特徴を有している。 On the other hand, a non-aqueous solvent containing PC or BC has a high vapor pressure and high oxidation potential, so that it is difficult to decompose, so that the amount of gas generated is small, and the battery is difficult to swell. Since it has a low freezing point, it has a feature of excellent low temperature characteristics.
また、負極材料として黒鉛、非晶質炭素などの炭素質材料を用いた負極は、コストが安価であり、サイクル寿命に優れていることから広く用いられているが、ＰＣやＢＣを含む非水溶媒系電解液を用いた場合、充電時のＰＣないしはＢＣの還元分解により電池の容量低下が発生する。特に、黒鉛化が進んだ高容量の炭素質物（天然黒鉛、人造黒鉛）では、ＰＣないしはＢＣがより激しく分解してしまい、充電が良好に進行しないという問題点が存在していた。 Negative electrodes using carbonaceous materials such as graphite and amorphous carbon as negative electrode materials are widely used because of their low cost and excellent cycle life, but non-water containing PC and BC. When a solvent-based electrolyte is used, the battery capacity is reduced due to reductive decomposition of PC or BC during charging. In particular, in high-capacity carbonaceous materials (natural graphite, artificial graphite) that have been graphitized, there has been a problem that PC or BC decomposes more violently and charging does not proceed well.
そこで、従来から、有機溶媒の還元分解を抑制するために、様々な化合物を非水溶媒系電解液に添加して、負極活物質が有機溶媒と直接反応しないように、不動態化層とも称される負極表面被膜（ＳＥＩ：Solid Electrolyte Interface. 以下、「ＳＥＩ表面被膜」という。）を制御する技術が重要となっている。例えば、下記特許文献１には、非水溶媒系二次電池の電解液中にビニレンカーボネート及びその誘導体から選択される少なくとも１種を添加し、これらの添加物により、最初の充電による負極へのリチウムの挿入前に負極活物質層上にＳＥＩ表面被膜を形成させ、リチウムイオンの周囲の溶媒分子の挿入を阻止するバリアーとして機能させるようになしたものが開示されている。 Therefore, conventionally, in order to suppress the reductive decomposition of the organic solvent, various compounds are added to the non-aqueous solvent electrolyte so that the negative electrode active material does not directly react with the organic solvent. Technology for controlling the negative electrode surface coating (SEI: Solid Electrolyte Interface. Hereinafter referred to as “SEI surface coating”) is important. For example, in Patent Document 1 below, at least one selected from vinylene carbonate and derivatives thereof is added to the electrolyte solution of a non-aqueous solvent secondary battery, and these additives add the negative electrode to the negative electrode by the first charge. It is disclosed that an SEI surface coating is formed on the negative electrode active material layer before insertion of lithium so as to function as a barrier that prevents insertion of solvent molecules around lithium ions.
また、同様の目的で、下記特許文献２には非水溶媒系電解液中に添加剤としてビニルエチレンカーボネート化合物を添加したものが、同じく下記特許文献３にはビニレンカーボネート化合物及びビニルエチレンカーボネート化合物を添加したものが、同じく下記特許文献４にはビニルエチレンカーボネートを含み、更にビニレンカーボネート、環状スルホン酸又は環状硫酸エステル、環状酸無水物からなる少なくとも１種を添加したものが、同じく下記特許文献５には環状酸無水物を添加したものが、同じく下記特許文献６には環状酸無水物及びビニルエチレンカーボネート化合物を添加したものが、それぞれ開示されている。 In addition, for the same purpose, the following Patent Document 2 includes a non-aqueous solvent electrolyte in which a vinyl ethylene carbonate compound is added as an additive, and the following Patent Document 3 includes a vinylene carbonate compound and a vinyl ethylene carbonate compound. In addition, the following Patent Document 4 contains vinyl ethylene carbonate, and further added at least one kind of vinylene carbonate, cyclic sulfonic acid or cyclic sulfate, and cyclic acid anhydride is also described in Patent Document 5 below. Is added with a cyclic acid anhydride, and the following Patent Document 6 discloses the addition of a cyclic acid anhydride and a vinyl ethylene carbonate compound.
このうち、環状酸無水物は、充電時における溶媒の還元分解の抑制には優れているが、単独添加ではＳＥＩ被膜の抵抗が高くなり、充放電特性が大きく低下するという欠点が存在していた。また、環状酸無水物を多量に添加すると、電解液のイオン伝導度が低下するほか、ＳＥＩ被膜の抵抗がより大きくなり、充放電特性が低下すると共に、充電保存中のガス発生が顕著となり、電池の膨れが大きいという問題点も存在していた。 Among these, cyclic acid anhydrides are excellent in suppressing reductive decomposition of the solvent during charging, but there is a drawback in that the addition of a single acid increases the resistance of the SEI film and the charge / discharge characteristics are greatly reduced. . In addition, when a large amount of cyclic acid anhydride is added, the ionic conductivity of the electrolytic solution is lowered, the resistance of the SEI film is further increased, the charge / discharge characteristics are lowered, and gas generation during charge storage becomes remarkable, There was also a problem that the swelling of the battery was large.
加えて、環状酸無水物を使用した非水系二次電池は、長期間高温保存すると、ＳＥＩ被膜に多量の重合物が堆積されるとともに、多量のガスが発生し、著しい容量低下を引き起こす。特に、黒鉛化が進んだ高容量の炭素質物を負極に用いた電池において、ＰＣやＢＣを含有する電解質の場合、高温での特性低下は顕著に現れる。 In addition, when a non-aqueous secondary battery using a cyclic acid anhydride is stored at a high temperature for a long period of time, a large amount of polymer is deposited on the SEI film and a large amount of gas is generated, causing a significant capacity reduction. In particular, in a battery using a high-capacity carbonaceous material with advanced graphitization as a negative electrode, in the case of an electrolyte containing PC or BC, the characteristic deterioration at a high temperature appears remarkably.
一方、非水溶媒系二次電池の電解液中にジオキソランとスクシンイミド化合物を添加することにより非水溶媒系二次電池の保存特性を向上させるようになしたものが下記特許文献７に開示されている。このスクシンイミド化合物は、環状酸無水物と同様に、負極で還元されて被膜を生成するが、溶媒の分解抑制能は環状酸無水物と比較して大きく劣る。 On the other hand, Patent Document 7 below discloses that the storage characteristics of a nonaqueous solvent secondary battery are improved by adding dioxolane and a succinimide compound to the electrolyte of the nonaqueous solvent secondary battery. Yes. Although this succinimide compound is reduced at the negative electrode to form a film, like the cyclic acid anhydride, the ability to suppress the decomposition of the solvent is greatly inferior to that of the cyclic acid anhydride.
本発明者は、上述のＳＥＩ表面被膜の生成機構につき種々検討を重ねた結果、非水溶媒系電解液中に環状酸無水物だけでなく、Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種を同時に添加すると、非水溶媒の分解を良好に防止することができ、しかもＳＥＩ表面被膜のインピーダンスを低下させ、初回放電容量を大きくでき、しかも、高負荷放電効率及び高温充電保存特性を向上させることができることを見出した。 As a result of various studies on the above-mentioned formation mechanism of the SEI surface coating, the present inventor has found that not only cyclic acid anhydrides but also N-alkyl succinimide compounds, N-alkenyl succinimide compounds, N -When at least one selected from arylsuccinimide compounds is added simultaneously, the decomposition of the non-aqueous solvent can be satisfactorily prevented, the impedance of the SEI surface coating can be lowered, the initial discharge capacity can be increased, and the high It has been found that load discharge efficiency and high temperature charge storage characteristics can be improved.
このような結果が得られる理由は、現在のところ定かではなく、今後の研究を待つ必要があるが、おそらくは上述のようなスクシンイミド化合物の添加により負極界面における環状酸無水物の継続的な還元分解反応が抑制されているために、本発明の効果が現れたものと推察される。 The reason why such a result is obtained is not clear at present, and it is necessary to wait for further research. Probably, the continuous reductive decomposition of cyclic acid anhydride at the negative electrode interface by the addition of the succinimide compound as described above. Since the reaction is suppressed, it is presumed that the effect of the present invention has appeared.
したがって、本願発明の目的は、ＳＥＩ表面被膜のインピーダンスを低下させ、初回放電容量が大きく、高負荷放電効率及び高温充電保存特性が向上した非水溶媒系二次電池を提供することにある。 Accordingly, an object of the present invention is to provide a non-aqueous solvent secondary battery in which the impedance of the SEI surface coating is reduced, the initial discharge capacity is large, the high load discharge efficiency and the high temperature charge storage characteristics are improved.
本発明の上記目的は以下の構成により達成し得る。すなわち、本願の請求項１に係る非水溶媒系二次電池の発明は、リチウムを可逆的に吸蔵・放出可能な正極活物質を含む正極と、リチウムを可逆的に吸蔵・放出可能な負極活物質を含む負極と、非水溶媒系電解液とを備えた非水溶媒系二次電池において、前記非水溶媒系電解液中に、
（１）環状酸無水物、及び
（２）Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種（以下、「スクシンイミド化合物」という。）、
を含有し、
前記環状酸無水物の含有量は、全電解質質量の０．０１〜１０質量％の範囲であり、
前記スクシンイミド化合物の含有量は、全電解質質量の０．０１〜１０質量％の範囲であり、
前記非水溶媒系電解液中の前記Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種と前記環状酸無水物との質量比は、１：２〜２：１の範囲である
ことを特徴とする。
The above object of the present invention can be achieved by the following configurations. That is, the invention of the nonaqueous solvent secondary battery according to claim 1 of the present application includes a positive electrode including a positive electrode active material capable of reversibly occluding and releasing lithium, and a negative electrode active capable of reversibly occluding and releasing lithium. In a non-aqueous solvent secondary battery comprising a negative electrode containing a substance and a non-aqueous solvent electrolyte, in the non-aqueous solvent electrolyte,
(1) cyclic acid anhydride, and (2) at least one selected from N-alkyl succinimide compounds, N-alkenyl succinimide compounds, and N-aryl succinimide compounds (hereinafter referred to as “succinimide compounds”),
Containing
The content of the cyclic acid anhydride is in the range of 0.01 to 10% by mass of the total electrolyte mass,
The content of the succinimide compound, Ri range der of 0.01 to 10% by weight of the total electrolyte weight,
The mass ratio of the cyclic acid anhydride to at least one selected from the N-alkyl succinimide compound, N-alkenyl succinimide compound and N-aryl succinimide compound in the non-aqueous solvent electrolyte is 1: 2 It is characterized by being in the range of 2: 1 .
本願発明は、前記非水溶媒系電解液中の前記スクシンイミド化合物と前記環状酸無水物との質量比は、１：２〜２：１の範囲であることを特徴とする。
これは、前記スクシンイミド化合物の前記環状酸無水物に対する含有割合が少ないと、ＳＥＩ被膜の抵抗が高くなり、充放電特性が大きく低下するので好ましくなく、また、前記スクシンイミド化合物の前記環状酸無水物に対する含有割合が多すぎても、非水溶媒の分解抑制効果が低下するからである。
また、非水溶媒系電解液を構成する非水溶媒（有機溶媒）としては、カーボネート類、ラクトン類、エーテル類、エステル類などが挙げられる。これら溶媒の２種類以上を混合して用いることもできる。これらの中ではカーボネート類、ラクトン類、エーテル類、ケトン類、エステル類などが好ましく、カーボネート類がさらに好適に用いられる。
The present invention is characterized in that a mass ratio of the succinimide compound and the cyclic acid anhydride in the non-aqueous solvent electrolyte is in a range of 1: 2 to 2: 1.
This is not preferable if the content ratio of the succinimide compound to the cyclic acid anhydride is small, because the resistance of the SEI film is increased and charge / discharge characteristics are greatly deteriorated, and the succinimide compound is not preferable for the cyclic acid anhydride. This is because even if the content ratio is too large, the effect of suppressing the decomposition of the non-aqueous solvent decreases.
As the non-aqueous solvent constituting the non-aqueous solvent electrolyte (organic solvent), carbonates, lactones, ethers, and esters. Two or more of these solvents can be used in combination. Among these, carbonates, lactones, ethers, ketones, esters and the like are preferable, and carbonates are more preferably used.
具体例としては、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）、ジメチルカーボネート（ＤＭＣ）、メチルエチルカーボネート（ＭＥＣ）、ジエチルカーボネート（ＤＥＣ）、γ−ブチロラクトン、γ−バレロラクトン、γ−ジメトキシエタン、テトラヒドロフラン、１，４−ジオキサン、ジエチルカーボネートなどを挙げることができ、充放電効率を高める点からはＥＣと鎖状カーボネートが好適に用いられる。 Specific examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), diethyl carbonate (DEC), γ-butyrolactone, and γ-valerolactone. , Γ-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, diethyl carbonate and the like, and EC and chain carbonate are preferably used from the viewpoint of improving the charge / discharge efficiency.
非水溶媒系電解液を構成する電解質には、過塩素酸リチウム（ＬｉＣｌＯ４）、六フッ化リン酸リチウム（ＬｉＰＦ６）、ホウフッ化リチウム（ＬｉＢＦ４）、六フッ化砒酸リチウム（ＬｉＡｓＦ６）、トリフルオロメチルスルホン酸リチウム（ＬｉＣＦ３ＳＯ３）、ビストリフルオロメチルスルホニルイミドリチウム（ＬｉＮ（ＣＦ３ＳＯ２）２）などのリチウム塩が挙げられる。中でもＬｉＰＦ６、ＬｉＢＦ４を用いるのが好ましく、前記非水溶媒に対する溶解量は、０．５〜２．０モル／ｌとするのが好ましい。 Examples of the electrolyte constituting the non-aqueous solvent electrolyte include lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), and lithium hexafluoroarsenate (LiAsF 6 ). And lithium salts such as lithium trifluoromethylsulfonate (LiCF 3 SO 3 ) and lithium bistrifluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ). Of these, LiPF 6 and LiBF 4 are preferably used, and the amount dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / l.
正極活物質には、ＬｉｘＭＯ２（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）、Ｌｉ０．５ＭｎＯ２、ＬｉＭｎＯ２、ＬｉＣｏｘＭｎｙＮｉｚＯ２（ｘ＋ｙ＋ｚ＝１）などが一種単独もしくは複数種を混合して用いられる。 As the positive electrode active material, a lithium transition metal composite oxide represented by Li x MO 2 (where M is at least one of Co, Ni, and Mn), that is, LiCoO 2 , LiNiO 2 , LiNi y Co 1− y O 2 (y = 0.01 to 0.99), Li 0.5 MnO 2 , LiMnO 2 , LiCo x Mn y Ni z O 2 (x + y + z = 1) or the like is used singly or in combination. It is done.
負極活物質には、リチウムを吸蔵・放出することが可能な炭素質物、珪素質物、金属酸化物からなる群から選択される少なくとも１種以上が用いられる。黒鉛化の進んだ炭素質物は高容量であるほか、本発明の効果がより大きく現れるために特に好ましい。 As the negative electrode active material, at least one selected from the group consisting of a carbonaceous material capable of inserting and extracting lithium, a siliconaceous material, and a metal oxide is used. A carbonaceous material that has been graphitized is particularly preferable because it has a high capacity and the effects of the present invention become more significant.
また、本願の請求項２に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、前記環状酸無水物が下記化学式で表されることを特徴とする。
また、本願の請求項３に係る発明は、前記請求項２に記載の非水溶媒系二次電池の発明において、前記環状酸無水物が、無水マレイン酸、無水フタル酸、無水コハク酸、無水メチルコハク酸、無水２，２−ジメチルコハク酸、無水グルタル酸、無水１，２−シクロヘキサンジカルボン酸、無水ｃｉｓ−１，２，３，６−テトラヒドロフタル酸、無水ｃｉｓ−５−ノルボルネン−ｅｎｄｏ−２，３−ジカルボン酸、無水フェニルコハク酸、無水２−フェニルグルタル酸、無水ノネニルコハク酸から選択された少なくとも１種であることを特徴とする。 The invention according to claim 3 of the present application is the invention of the non-aqueous solvent secondary battery according to claim 2, wherein the cyclic acid anhydride is maleic anhydride, phthalic anhydride, succinic anhydride, anhydrous Methyl succinic acid, 2,2-dimethyl succinic anhydride, glutaric anhydride, 1,2-cyclohexanedicarboxylic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, cis-5-norbornene-endo-2 , 3-dicarboxylic acid, phenyl succinic anhydride, 2-phenyl glutaric anhydride, and nonenyl succinic anhydride.
また、本願の請求項４に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、前記非水溶媒系電解液中の環状酸無水物の含有量は０．０５質量％以上５質量％以下であることを特徴とする。
In the invention, in the non-aqueous solvent secondary battery according to claim 1, content 0.0 5 mass of cyclic acid anhydrides of the nonaqueous solvent system electrolytic solution according to claim 4 of the present application you wherein the percent 5 mass% or less.
係る前記環状酸無水物の含有量は、０．０１質量％未満であると前記環状酸無水物添加の効果が実質的に認められず、また、１０質量％を超えても、その分だけ電解質の溶解量が減って電解質濃度が低下し、非水溶媒系電解液の電気伝導度が減少するために好ましくない。より好ましくは、前記環状酸無水物の含有量は、全電解質質量の０．０５〜５質量％である。 When the content of the cyclic acid anhydride is less than 0.01% by mass, the effect of adding the cyclic acid anhydride is not substantially recognized. This is not preferable because the electrolyte concentration is reduced by reducing the amount of the solution and the electrical conductivity of the non-aqueous solvent electrolyte is reduced. More preferably, the content of the cyclic acid anhydride is 0.05 to 5% by mass of the total electrolyte mass.
また、本願の請求項５に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、前記スクシンイミド化合物におけるアルキル基、アルケニル基又はアリール基に含まれる炭素数は１以上１２以下であることを特徴とする。
The invention according to claim 5 of the present application is the non-aqueous solvent secondary battery according to claim 1, wherein the alkyl group, alkenyl group or aryl group in the succinimide compound has 1 to 12 carbon atoms. It is characterized by being.
また、本願の請求項６に係る発明は、前記請求項５に記載の非水溶媒系二次電池において、前記Ｎ−アルキルスクシンイミド化合物がＮ−メチルスクシンイミド、Ｎ−エチルスクシンイミド、Ｎ−イソプロピルスクシンイミド、Ｎ−シクロヘキシルスクシンイミド、Ｎ−イソブチルスクシンイミド、Ｎ−ｔｅｒｔ−アミルスクシンイミドから選択された少なくとも１種であり、前記アルケニルスクシンイミド化合物がＮ−ビニルスクシンイミド、Ｎ−アリルスクシンイミドから選択された少なくとも１種であり、また、前記アリールスクシンイミド化合物がＮ−フェニルスクシンイミドであることを特徴とする。
The invention according to claim 6 of the present application is the nonaqueous solvent secondary battery according to claim 5 , wherein the N-alkylsuccinimide compound is N-methylsuccinimide, N-ethylsuccinimide, N-isopropylsuccinimide, At least one selected from N-cyclohexyl succinimide, N-isobutyl succinimide, N-tert-amyl succinimide, and the alkenyl succinimide compound is at least one selected from N-vinyl succinimide and N-allyl succinimide, The aryl succinimide compound is N-phenyl succinimide.
また、本願の請求項７に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、前記スクシンイミド化合物の含有量は、全電解質質量の０．０５〜５質量％の範囲であることを特徴とする。
The invention according to claim 7 of the present application, in the non-aqueous solvent secondary battery according to claim 1, the content of the succinimide compound is in the range of 0.0 5 to 5 wt% based on the entire mass of the electrolyte it characterized in that it is.
前記スクシンイミド化合物の含有量が全電解質質量の０．０１％未満であると添加の効果が表れず、また、１０質量％を超えて添加してもその効果が飽和するだけでなく、その分だけ電解液溶媒の含有量が減るので、イオン伝導度が減るため好ましくない。より好ましくは、前記スクシンイミド化合物の含有量は、全電解質質量の０．０５〜５質量％である。 If the content of the succinimide compound is less than 0.01% of the total electrolyte mass, the effect of addition does not appear, and the addition of more than 10% by mass not only saturates the effect, but only by that amount. Since the content of the electrolyte solvent decreases, the ionic conductivity decreases, which is not preferable. More preferably, content of the said succinimide compound is 0.05-5 mass% of the total electrolyte mass.
また、本願の請求項８に係る発明は、前記請求項１に係る非水溶媒系二次電池において、前記負極活物質はＸ線回折における格子面（００２面）のｄ値が０．３４０ｎｍ以下である炭素質物であり、前記非水溶媒はＰＣあるいはＢＣを含むことを特徴とする。炭素質物質は結晶化が進むとＸ線回折における格子面（００２面）のｄ値が小さくなり、結晶化が進んだ天然黒鉛や人造黒鉛等は前記ｄ値が０．３４０ｎｍ以下となるが、本発明は負極がこのような高度に結晶化が進んだ炭素質物質を含む場合においても適用可能であり、この場合においては高容量の非水溶媒系二次電池が得られる。
The invention according to claim 8 of the present application is the nonaqueous solvent secondary battery according to claim 1, wherein the negative electrode active material has a d-value of 0.340 nm or less on the lattice plane (002 plane) in X-ray diffraction. And the non-aqueous solvent contains PC or BC. As the crystallization of the carbonaceous material proceeds, the d value of the lattice plane (002 plane) in X-ray diffraction becomes smaller, and natural graphite and artificial graphite that have been crystallized have the d value of 0.340 nm or less. The present invention can also be applied to the case where the negative electrode contains such a highly crystallized carbonaceous material. In this case, a high-capacity nonaqueous solvent secondary battery can be obtained.
また、本願の請求項９に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、前記非水溶媒系電解液は、ゲル化されていることを特徴とする。ゲル化されている場合は、環状酸無水物の酸化分解によって発生したガスが正負極板間に滞留しやすく、有効極板面積の低下による容量低下が著しいことから、本発明の効果が大きく表れる。
The invention according to claim 9 of the present application is characterized in that, in the non-aqueous solvent secondary battery according to claim 1, the non-aqueous solvent electrolyte is gelled. When gelled, the gas generated by the oxidative decomposition of the cyclic acid anhydride tends to stay between the positive and negative electrode plates, and the capacity reduction due to the reduction of the effective electrode plate area is significant, so the effect of the present invention is greatly exhibited. .
更に、前記非水溶媒系電解液がゲル化されている場合は、負極活物質表面にポリマー成分が付着しているため、通常負極界面に生じるＳＥＩ被膜の抵抗が大きくなり、液状電解質を使用した非水溶媒系二次電池よりも著しく特性低下が引き起こされるが、このゲル化による抵抗増大作用は、非水溶媒系電解液中に前記環状酸無水物とスクシンイミド化合物を添加したことによるＳＥＩ被膜の抵抗低下作用と相殺されるため、良好な特性を有するゲル化された非水溶媒系二次電池が得られるようになる。 Furthermore, when the non-aqueous solvent electrolyte is gelled, the polymer component adheres to the surface of the negative electrode active material, so the resistance of the SEI film that usually occurs at the negative electrode interface increases, and a liquid electrolyte is used. Although the characteristic deterioration is caused more significantly than that of the non-aqueous solvent type secondary battery, the increase in resistance due to the gelation is caused by the addition of the cyclic acid anhydride and the succinimide compound to the non-aqueous solvent type electrolyte. Since this cancels out the resistance lowering action, a gelled non-aqueous solvent secondary battery having good characteristics can be obtained.
ゲル状電解質において、電解液を保持する高分子としては、アルキレンオキシド系高分子や、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体のようなフッ素系高分子等の高分子が挙げられる。このような高分子材料を用いてゲル状電解質を形成する方法は、前記電解液をポリエチレンオキシド、ポリプロピレンオキシド、ポリアルキレンオキシドのイソシアネート架橋体等の重合体などに浸漬することにより得ることができる。 In the gel electrolyte, examples of the polymer holding the electrolytic solution include polymers such as an alkylene oxide polymer and a fluorine polymer such as a polyvinylidene fluoride-hexafluoropropylene copolymer. A method of forming a gel electrolyte using such a polymer material can be obtained by immersing the electrolytic solution in a polymer such as polyethylene oxide, polypropylene oxide, or a cross-linked isocyanate of polyalkylene oxide.
また、重合性ゲル化剤を含有する電解液に紫外線硬化や熱硬化などの重合処理を施す方法や、常温でゲル状電解質を形成する高分子を電解液中に高温溶解したものを冷却する方法も好ましく用いられる。重合性ゲル化剤含有電解液を用いる場合、重合性ゲル化剤としては、例えば、アクリロイル基、メタクリロイル基、ビニル基、アリル基等の不飽和二重結合を有するものや、エポキシ、オキセタン、ホルマール等のカチオン重合性の環状エーテル基を有するものが挙げられる。 In addition, a method of subjecting an electrolytic solution containing a polymerizable gelling agent to a polymerization treatment such as ultraviolet curing or thermosetting, or a method of cooling a solution obtained by dissolving a polymer that forms a gel electrolyte at room temperature at a high temperature. Are also preferably used. When the polymerizable gelling agent-containing electrolyte is used, examples of the polymerizable gelling agent include those having an unsaturated double bond such as acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy, oxetane, formal. And those having a cationically polymerizable cyclic ether group.
具体的にはアクリル酸、アクリル酸メチル、アクリル酸エチル、エトキシエチルアクリレート、メトキシエチルアクリレート、エトキシエトキシエチルアクリレート、ポリエチレングリコールモノアクリレート、エトキシエチルメタクリレート、エトキシエチルメタクリレート、ポリエチレングリコールモノメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレート、グリシジルアクリレート、アリルアクリレート、アクリロニトリル、ジエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、ポリエチレングリコールジメタクリレート、ポリプロピレングリコールジアクリレート、ポリプロピレングリコールジメタクリレート、ポリアルキレングリコールジメタクリレート、ポリアルキレングリコールジメタクリレート、トリメチロールプロパンアルコキシレートトリアクリレート、ペンタエリスリトールアルコキシレートテトラアクリレート、ペンタエリスリトールアルコキシレートテトラアクリレートなどの不飽和二重結合を有するモノマー、メチルメタクリレートと（３−エチル−３−オキセタニル）メチルアクリレートの共重合ポリマー（分子量約４０万）、テトラエチレングリコールビスオキセタンなどの環状エーテル基含有化合物などが挙げられる。 Specifically, acrylic acid, methyl acrylate, ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate, ethoxyethyl methacrylate, ethoxyethyl methacrylate, polyethylene glycol monomethacrylate, N, N- Diethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polyalkylene glycol dimethacrylate Monomers having an unsaturated double bond, such as methyl methacrylate, (3-ethyl-3), polyalkylene glycol dimethacrylate, trimethylolpropane alkoxylate triacrylate, pentaerythritol alkoxylate tetraacrylate, pentaerythritol alkoxylate tetraacrylate -Oxetanyl) methyl acrylate copolymer (molecular weight of about 400,000), cyclic ether group-containing compounds such as tetraethylene glycol bisoxetane, and the like.
不飽和結合を有するモノマーは熱、紫外線、電子線などによって重合させることができるが、反応を効果的に進行させるため、電解液に重合開始剤を入れておくこともできる。重合開始剤としては、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシクメン、ラウロイルパーオキサイド、ジ−２−エチルヘキシルパーオキシジカーボネート、ｔ−ブチルパーオキシピバレート、ｔ−ヘキシルパーオキシイソプロピルモノカーボネートなどの有機過酸化物を使用できる。また、環状エーテル基含有化合物は、電解液中のＬｉ＋や微量のＨ＋によって、熱あるいは充放電により重合が開始される。 A monomer having an unsaturated bond can be polymerized by heat, ultraviolet light, electron beam, or the like, but a polymerization initiator may be added to the electrolytic solution in order to effectively advance the reaction. Examples of the polymerization initiator include organic compounds such as benzoyl peroxide, t-butyl peroxycumene, lauroyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, and t-hexyl peroxyisopropyl monocarbonate. Peroxides can be used. In addition, the cyclic ether group-containing compound is polymerized by heat or charge / discharge due to Li + or a small amount of H + in the electrolytic solution.
一方、常温でゲル状電解質を形成する高分子を電解液中に高温溶解したものを冷却する方法は、このような高分子としては、電解液に対してゲルを形成し電池材料として安定なものであればどのようなものであってもよい。例えば、ポリビニルピリジン、ポリ−Ｎ−ビニルピロリドンなどの環を有するポリマー；ポリアクリル酸メチル、ポリアクリル酸エチルなどのアクリル誘導体ポリマー；ポリフッ化ビニル、ポリフッ化ビニリデンなどのフッ素系樹脂；ポリアクリロニトリル、ポリビニリデンシアニドなどのＣＮ基含有ポリマー；ポリ酢酸ビニル、ポリビニルアルコールなどのポリビニルアルコール系ポリマー；ポリ塩化ビニル、ポリ塩化ビニリデンなどのハロゲン含有ポリマーなどが挙げられる。また、上記の高分子などとの混合物、変成体、誘導体、ランダム共重合体、グラフト共重合体、ブロック共重合体などであっても使用できる。これらの高分子の質量平均分子量は通常１０，０００〜５，０００，０００の範囲である。分子量が低いとゲルを形成しにくくなる。分子量が高いと粘度が高くなりすぎて取り扱いが困難となる。 On the other hand, a method of cooling a polymer that forms a gel electrolyte at room temperature at a high temperature is dissolved in an electrolyte solution. As such a polymer, a gel is formed with respect to the electrolyte solution and is stable as a battery material. Anything may be used. For example, polymers having a ring such as polyvinyl pyridine and poly-N-vinyl pyrrolidone; acrylic derivative polymers such as polymethyl acrylate and polyethyl acrylate; fluororesins such as polyvinyl fluoride and polyvinylidene fluoride; polyacrylonitrile, poly CN group-containing polymers such as vinylidene cyanide; polyvinyl alcohol polymers such as polyvinyl acetate and polyvinyl alcohol; halogen-containing polymers such as polyvinyl chloride and polyvinylidene chloride. Moreover, it can be used even if it is a mixture with said polymer | macromolecule, a modified body, a derivative, a random copolymer, a graft copolymer, a block copolymer, etc. The mass average molecular weight of these polymers is usually in the range of 10,000 to 5,000,000. When the molecular weight is low, it is difficult to form a gel. If the molecular weight is high, the viscosity becomes too high and handling becomes difficult.
また、本願の請求項１０に係る発明は、前記請求項９に記載の非水溶媒系二次電池において、前記ゲル化されている非水溶媒系電解液における電解液の含有量は、ゲル化されている非水溶媒系電解液の総量に対して５０質量％以上９９．５質量％以下であることを特徴とし、同じく請求項１１に係る発明は、前記請求項１０に記載の非水溶媒系二次電池において、記ゲル化されている非水溶媒系電解液における電解液の含有量は、ゲル化されている非水溶媒系電解液の総量に対して７５質量％以上９９．５質量％以下であることを特徴とする。
The invention according to claim 10 of the present application is the nonaqueous solvent secondary battery according to claim 9 , wherein the content of the electrolyte in the gelled nonaqueous solvent electrolyte is gelled. 50 mass% or more and 99.5 mass% or less with respect to the total amount of the nonaqueous solvent type electrolyte solution currently used, The invention which concerns on Claim 11 is the nonaqueous solvent of the said Claim 10 similarly In the secondary battery, the content of the electrolyte in the gelled non-aqueous solvent electrolyte is 75% by mass or more and 99.5% by mass with respect to the total amount of the gelled non-aqueous solvent electrolyte. % Or less.
ゲル化されている非水溶媒系電解液における電解液の含有量が５０質量％未満と少なすぎるとイオン伝導度が低下して高負荷放電効率が悪化する。より好ましくはゲル状電解質の総量に対して７５質量％以上である。さらに、電解液の含有量が、９９．５質量％を超えると、電解液の保持が困難となり、液漏れや漏液が生じやすくなると共に、ゲル化されている非水溶媒系電解液の機械的強度が得られない。 If the content of the electrolytic solution in the gelled non-aqueous solvent electrolytic solution is too small, such as less than 50% by mass, the ionic conductivity is lowered and the high-load discharge efficiency is deteriorated. More preferably, it is 75 mass% or more with respect to the total amount of the gel electrolyte. Furthermore, when the content of the electrolytic solution exceeds 99.5% by mass, it becomes difficult to hold the electrolytic solution, and liquid leakage or leakage is likely to occur, and the gelled nonaqueous solvent electrolytic solution machine Strength cannot be obtained.
また、本願の請求項１２に係る発明は、前記請求項１に記載の非水溶媒系二次電池において、更にラミネート外装体を有していることを特徴とする。このような構成の非水溶媒系二次電池によれば、外装の質量を小さくでき、しかも厚さも薄くできるために、小型軽量の非水溶媒系二次電池を得ることができる。また、ラミネート外装体を用いる場合は、膨れの影響が顕著に現れるため、本発明の効果が大きく表れる。
The invention according to claim 12 of the present application is characterized in that the nonaqueous solvent secondary battery according to claim 1 further includes a laminate outer package. According to the non-aqueous solvent secondary battery having such a configuration, the mass of the outer casing can be reduced and the thickness can be reduced, so that a small and lightweight non-aqueous solvent secondary battery can be obtained. In addition, when the laminate outer package is used, the effect of the present invention is greatly exhibited because the influence of swelling appears remarkably.
本発明は、非水溶媒系二次電池において、前記非水溶媒系電解液中に、
（１）環状酸無水物、及び
（２）スクシンイミド化合物、
を含有させたため、ＳＥＩ被膜のインピーダンスが非常に低くなると共に、以下に詳細に述べるように、初回放電容量が大きくなり、高負荷放電効率が向上し、かつ長期間の高温充電保存後においても容量低下の小さい非水溶媒系二次電池が得られる。
In the non-aqueous solvent secondary battery, the present invention, in the non-aqueous solvent electrolyte,
(1) a cyclic acid anhydride, and (2) a succinimide compound,
As a result, the impedance of the SEI film becomes very low, and as will be described in detail below, the initial discharge capacity is increased, the high-load discharge efficiency is improved, and the capacity is maintained even after long-term high-temperature storage. A non-aqueous solvent secondary battery with a small decrease is obtained.
以下、本願発明を実施するための最良の形態を実施例及び比較例を用いて詳細に説明するが、まず最初に実施例及び比較例に共通する非水溶媒系二次電池の具体的製造方法について説明する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described in detail using examples and comparative examples. First, a specific method for producing a nonaqueous solvent secondary battery common to the examples and comparative examples will be described. Will be described.
<正極板の作製>
ＬｉＣｏＯ２からなる正極活物質をアセチレンブラック、グラファイト等の炭素系導電剤（例えば５質量％）と、ポリビニリデンフルオライド（ＰＶｄＦ）よりなる結着剤（例えば３質量％）等を、Ｎ−メチルピロリドンからなる有機溶剤に溶解したものを混合して、活物質スラリーあるいは活物質ペーストとする。これらの活物質スラリーあるいは活物質ペーストを、スラリーの場合はダイコーター、ドクターブレード等を用いて、ペーストの場合はローラコーティング法等により正極芯体（例えば、厚みが１５μｍのアルミニウム箔あるいはアルミニウムメッシュ）の両面に均一に塗付して、活物質層を塗布した正極板を形成する。この後、活物質層を塗布した正極板を乾燥機中に通過させて、スラリーあるいはペースト作製時に必要であった有機溶剤を除去して乾燥させる。乾燥後、この乾燥正極板をロールプレス機により圧延して、厚みが０．１５ｍｍの正極板とする。
<Preparation of positive electrode plate>
A positive electrode active material made of LiCoO 2 is a carbon-based conductive agent (for example, 5% by mass) such as acetylene black and graphite, and a binder (for example, 3% by mass) made of polyvinylidene fluoride (PVdF) is N-methyl. A material dissolved in an organic solvent composed of pyrrolidone is mixed to obtain an active material slurry or an active material paste. These active material slurries or active material pastes use a die coater, doctor blade, etc. in the case of slurry, and in the case of paste, a positive electrode core (for example, an aluminum foil or aluminum mesh having a thickness of 15 μm) by a roller coating method or the like. A positive electrode plate coated with an active material layer is formed by uniformly applying to both sides. Thereafter, the positive electrode plate coated with the active material layer is passed through a drier to remove the organic solvent necessary for the preparation of the slurry or paste and dry it. After drying, this dry positive electrode plate is rolled by a roll press to obtain a positive electrode plate having a thickness of 0.15 mm.
<負極板の作製>
天然黒鉛（ｄ（００２）値＝０．３３５ｎｍ）よりなる負極活物質、ポリビニリデンフルオライド（ＰＶｄＦ）よりなる結着剤（例えば３質量％）等と、Ｎ−メチルピロリドンからなる有機溶剤に溶解したものを混合して、スラリーあるいはペーストとする。これらのスラリーあるいはペーストを、スラリーの場合はダイコーター、ドクターブレード等を用いて、ペーストの場合はローラコーティング法等により負極芯体（例えば、厚みが１０μｍの銅箔）の両面の全面にわたって均一に塗布して、活物質層を塗布した負極板を形成する。この後、活物質層を塗布した負極板を乾燥機中に通過させて、スラリーあるいはペースト作製時に必要であった有機溶剤を除去して乾燥させる。乾燥後、この乾燥負極板をロールプレス機により圧延して、厚みが０．１４ｍｍの負極板とする。
<Preparation of negative electrode plate>
Dissolved in a negative electrode active material made of natural graphite (d (002) value = 0.335 nm), a binder (for example, 3% by mass) made of polyvinylidene fluoride (PVdF), etc., and an organic solvent made of N-methylpyrrolidone These are mixed to form a slurry or paste. These slurries or pastes are uniformly applied over the entire surface of the negative electrode core (for example, a copper foil having a thickness of 10 μm) by using a die coater, a doctor blade or the like in the case of a slurry, or by a roller coating method in the case of a paste. The negative electrode plate which apply | coated and applied the active material layer is formed. Thereafter, the negative electrode plate coated with the active material layer is passed through a drier to remove the organic solvent that was necessary when the slurry or paste was prepared, and then dried. After drying, the dried negative electrode plate is rolled by a roll press to obtain a negative electrode plate having a thickness of 0.14 mm.
<電極体の作製>
上述のようにして作製した正極板と負極板を、有機溶媒との反応性が低く、かつ安価なポリオレフイン系樹脂からなる微多孔膜（例えば、厚みが０．０２０ｍｍ）を間にし、かつ、各極板の幅方向の中心線を−致させて重ね合わせる。この後、巻き取り機により捲回する。この後、最外周をテープ止めして渦巻状電極体とする。上述のようにして作製した電極体をアルミラミネートにより構成された外装体にそれぞれ挿入する。ついで、電極体より延出した正極集電タブ、負極集電タブを外装体と共に溶着する。
<Production of electrode body>
The positive electrode plate and the negative electrode plate produced as described above are each provided with a microporous film (for example, a thickness of 0.020 mm) made of a polyolefin resin that is low in reactivity with an organic solvent and inexpensive, and each The center line in the width direction of the electrode plate is made to coincide and overlap. Then, it is wound by a winder. Thereafter, the outermost periphery is taped to form a spiral electrode body. The electrode bodies produced as described above are inserted into the exterior bodies made of aluminum laminate. Subsequently, the positive electrode current collection tab and the negative electrode current collection tab extended from the electrode body are welded with an exterior body.
<電解質の作製>
ＥＣ／ＰＣ／ＤＥＣ（２０／１０／７０）の質量比で混合した溶媒に、１．０ＭとなるようにＬｉＰＦ６を溶解させて電解液を作製する。添加化合物の種類と量は、表中に記載したとおりであり、全て電解液質量に対する質量比である。
<Preparation of electrolyte>
LiPF 6 is dissolved in a solvent mixed at a mass ratio of EC / PC / DEC (20/10/70) so as to be 1.0 M to prepare an electrolytic solution. The types and amounts of the additive compounds are as described in the table, and all are mass ratios relative to the electrolyte solution mass.
ゲル状電解質の作製においては、上記電解液に、モノマーとしてテトラエチレングリコールジメタクリレート８質量％を加え、重合開始剤としてｔ−ブチルパーオキシピバレート０．３質量％を加えてプレゲルを作製する。添加化合物の種類と量は、表中に記載したとおりであり、全て電解質質量（電解液＋モノマー＋重合開始剤）に対する質量比である。 In the preparation of the gel electrolyte, a pregel is prepared by adding 8% by mass of tetraethylene glycol dimethacrylate as a monomer and 0.3% by mass of t-butyl peroxypivalate as a polymerization initiator to the above electrolyte. The types and amounts of the additive compounds are as described in the table, and all are mass ratios with respect to the electrolyte mass (electrolytic solution + monomer + polymerization initiator).
<電池の作製>
次いで、各種非水溶媒系電解液を外装体の開口部より必要量注液した後シールして、実施例及び比較例の全てについて設計容量が５００ｍＡｈのリチウムイオン非水溶媒系二次電池を作製した。ゲル状電解質電池の作製は、プレゲルを必要量注液した後、開口部をシールして、７０℃で３時間加熱して重合させ、リチウムポリマー非水溶媒系二次電池を作製した。
<Production of battery>
Next, various non-aqueous solvent electrolytes were injected through the openings of the outer package, and then sealed to produce lithium ion non-aqueous solvent secondary batteries with a design capacity of 500 mAh for all of the examples and comparative examples. did. The gel electrolyte battery was prepared by pouring the required amount of pregel, sealing the opening, and polymerizing by heating at 70 ° C. for 3 hours to prepare a lithium polymer non-aqueous solvent secondary battery.
（実施例１〜１４、比較例１〜７）
まず、液状非水溶媒系電解質を使用し、
（１）実施例１〜８の非水溶媒系二次電池として、スクシンイミド化合物としてＮ−メチルスクシンイミドを使用し、環状酸無水物の種類を変えて８種類の非水溶媒系二次電池を作製し、同じく、
（２）実施例９〜１２の非水溶媒系二次電池として、環状酸無水物として無水コハク酸を使用し、スクシンイミド化合物の種類を変えて４種類の非水溶媒系二次電池を作製した。
(Examples 1-14, Comparative Examples 1-7)
First, using a liquid non-aqueous solvent electrolyte,
(1) As nonaqueous solvent type secondary batteries of Examples 1 to 8, N-methylsuccinimide was used as a succinimide compound, and eight kinds of nonaqueous solvent type secondary batteries were produced by changing the type of cyclic acid anhydride. And
(2) As the non-aqueous solvent type secondary batteries of Examples 9 to 12, succinic anhydride was used as the cyclic acid anhydride, and four kinds of non-aqueous solvent type secondary batteries were produced by changing the type of the succinimide compound. .
また、ゲル状非水溶媒系電解質を使用し、
（３）実施例１３及び１４の非水溶媒系二次電池として、環状酸無水物として無水コハク酸を使用し、スクシンイミド化合物の種類を変えて２種類の非水溶媒系二次電池を作製した。
Also, using a gel-like non-aqueous solvent electrolyte,
(3) As the nonaqueous solvent secondary batteries of Examples 13 and 14, succinic anhydride was used as the cyclic acid anhydride, and two types of nonaqueous solvent secondary batteries were produced by changing the type of succinimide compound. .
同様に、液状非水溶媒系電解質を使用し、
（４）比較例１〜３として、スクシンイミド化合物は添加せず、環状酸無水物の種類を変えて３種類の非水溶媒系二次電池を作製し、
（５）比較例４及び５として、環状酸無水物は添加せず、スクシンイミド化合物の種類を変えて２種類の非水溶媒系二次電池を作製し、
（６）比較例６として、スクシンイミド化合物及び環状酸無水物共に添加せずに非水溶媒系二次電池を作製し、更に、
ゲル状非水溶媒系電解質を使用し、
（７）比較例７として、スクシンイミド化合物は添加せず、環状酸無水物として無水コハク酸を添加した非水溶媒系二次電池を作製した。
Similarly, using a liquid non-aqueous solvent electrolyte,
(4) As Comparative Examples 1 to 3, no succinimide compound was added, and the types of cyclic acid anhydrides were changed to produce three types of nonaqueous solvent type secondary batteries.
(5) As Comparative Examples 4 and 5, cyclic acid anhydrides were not added, and the types of succinimide compounds were changed to produce two types of nonaqueous solvent type secondary batteries.
(6) As Comparative Example 6, a non-aqueous solvent secondary battery was prepared without adding both the succinimide compound and the cyclic acid anhydride,
Using a gel-like non-aqueous solvent electrolyte,
(7) As Comparative Example 7, a non-aqueous solvent secondary battery was prepared in which succinimide compound was not added and succinic anhydride was added as a cyclic acid anhydride.
なお、上記実施例１〜１４及び比較例１〜７の全てについて、環状酸無水物を添加する場合は全非水溶媒系電解質質量に対して１．５質量％となるように添加し、スクシンイミド化合物を添加する場合は全非水溶媒系電解質質量に対して１．０質量％となるように添加した。 In addition, about all of said Examples 1-14 and Comparative Examples 1-7, when adding a cyclic acid anhydride, it adds so that it may become 1.5 mass% with respect to the total nonaqueous solvent type electrolyte mass, and succinimide When adding a compound, it added so that it might become 1.0 mass% with respect to the total nonaqueous solvent type electrolyte mass.
<充放電条件>
上述のようにして作製した実施例１〜１４及び比較例１〜７の各非水溶媒系二次電池のそれぞれについて、以下に示した充放電条件下で各種充放電試験を行った。
<Charging / discharging conditions>
For each of the nonaqueous solvent secondary batteries of Examples 1 to 14 and Comparative Examples 1 to 7 produced as described above, various charge / discharge tests were performed under the following charge / discharge conditions.
<初回放電容量の測定>
まず最初に、各電池について、２５℃において、１Ｉｔ（１Ｃ）＝５００ｍＡの定電流で充電し、電池電圧が４．２Ｖに達した後は４．２Ｖの定電圧で３時間充電した。その後、１Ｉｔの定電流で電池電圧が２．７５Ｖに達するまで放電を行い、この時の放電容量を初回放電容量として求めた。結果を表１に示す。
<Measurement of initial discharge capacity>
First, each battery was charged at 25 ° C. with a constant current of 1 It (1C) = 500 mA, and after the battery voltage reached 4.2 V, it was charged with a constant voltage of 4.2 V for 3 hours. Thereafter, discharging was performed at a constant current of 1 It until the battery voltage reached 2.75 V, and the discharge capacity at this time was determined as the initial discharge capacity. The results are shown in Table 1.
<高負荷放電効率の測定>
初回放電容量を測定した各電池について、２５℃において、１Ｉｔ＝５００ｍＡの定電流で充電し、電池電圧が４．２Ｖに達した後は４．２Ｖの定電圧で３時間充電した。その後、０．２Ｉｔ＝１００ｍＡの定電流で電池電圧が２．７５Ｖになるまで放電を行い、このときの放電容量を０．２Ｉｔ放電容量として求めた。別途同様に充電した電池について３Ｉｔ＝１５００ｍＡの定電流で電池電圧が２．７５Ｖとなるまで放電させてこの時の放電容量を３Ｉｔ放電容量として求め、以下の計算式により高負荷放電効率を求めた。結果を表１にまとめて示す。
高負荷放電効率（％）＝（３Ｉｔ放電容量／０．２Ｉｔ放電容量）×１００
<Measurement of high load discharge efficiency>
Each battery whose initial discharge capacity was measured was charged with a constant current of 1 It = 500 mA at 25 ° C., and after the battery voltage reached 4.2 V, it was charged with a constant voltage of 4.2 V for 3 hours. Thereafter, discharging was performed at a constant current of 0.2 It = 100 mA until the battery voltage reached 2.75 V, and the discharge capacity at this time was determined as the 0.2 It discharge capacity. A separately charged battery was discharged at a constant current of 3 It = 1500 mA until the battery voltage reached 2.75 V, the discharge capacity at this time was determined as the 3 It discharge capacity, and the high load discharge efficiency was determined by the following formula: . The results are summarized in Table 1.
High load discharge efficiency (%) = (3 It discharge capacity / 0.2 It discharge capacity) × 100
<高温充電保存特性の測定>
初回放電容量を測定した各電池について、２５℃において、１Ｉｔ＝５００ｍＡの定電流で充電し、電池電圧が４．２Ｖに達した後は４．２Ｖの定電圧で３時間充電した。その後、１Ｉｔ＝５００ｍＡで電池電圧が２．７５Ｖとなるまで放電を行い、このときの放電容量を保存前放電容量として求めた。別途同様に充電した電池について８０℃の高温条件下に５日間放置し、２５℃において１Ｉｔの定電流で電池電圧が２．７５Ｖとなるまで放電を行い、このときの放電容量を保存後放電容量として求め、以下の計算式により容量維持率を求めた。結果をまとめて表１に示す。
容量維持率（％）＝（保存後放電容量／保存前放電容量）×１００
<Measurement of high-temperature storage characteristics>
Each battery whose initial discharge capacity was measured was charged with a constant current of 1 It = 500 mA at 25 ° C., and after the battery voltage reached 4.2 V, it was charged with a constant voltage of 4.2 V for 3 hours. Thereafter, discharging was performed at 1 It = 500 mA until the battery voltage reached 2.75 V, and the discharge capacity at this time was determined as the discharge capacity before storage. Separately charged batteries were left under high temperature conditions of 80 ° C. for 5 days and discharged at 25 ° C. at a constant current of 1 It until the battery voltage reached 2.75 V. The discharge capacity at this time was stored and then discharged. As a result, the capacity retention rate was calculated by the following calculation formula. The results are summarized in Table 1.
Capacity retention rate (%) = (discharge capacity after storage / discharge capacity before storage) × 100
表１の結果から、液状非水溶媒系電解質を使用した場合、環状酸無水物及びスクシンイミド化合物の両者共に含まない比較例６の非水溶媒系二次電池を基準とすると以下のことが分かる。
（ａ）スクシンイミド化合物のみを含み、環状酸無水物を含まない比較例４及び５の非水溶媒系二次電池では、初回放電容量は比較例６のものよりもわずかによい結果が得られているが、高負荷放電効率及び高温充電保存特性は比較例６のものと同程度となっている。
（ｂ）環状酸無水物のみを含み、スクシンイミド化合物を含まない比較例１〜３の非水溶媒系二次電池では、初回放電容量は比較例６のものよりも増大しているが、高負荷放電効率及び高温充電保存特性は大幅に悪化している。
（ｃ）環状酸無水物及びスクシンイミド化合物の両者を含む実施例１〜１２の非水溶媒系二次電池では、初回放電容量は比較例６のものよりも大で比較例１〜３のものと同程度であるが、高負荷放電効率及び高温充電保存特性は比較例６のものとほぼ同程度の結果が得られている。
From the results of Table 1, the following can be seen from the nonaqueous solvent secondary battery of Comparative Example 6 that does not contain both the cyclic acid anhydride and the succinimide compound when the liquid nonaqueous solvent electrolyte is used.
(A) In the nonaqueous solvent type secondary batteries of Comparative Examples 4 and 5 containing only the succinimide compound and no cyclic acid anhydride, the initial discharge capacity was slightly better than that of Comparative Example 6. However, the high-load discharge efficiency and high-temperature charge storage characteristics are comparable to those of Comparative Example 6.
(B) In the nonaqueous solvent type secondary batteries of Comparative Examples 1 to 3 containing only the cyclic acid anhydride and not containing the succinimide compound, the initial discharge capacity was higher than that of Comparative Example 6, but the load was high. Discharge efficiency and high temperature charge storage characteristics are greatly deteriorated.
(C) In the nonaqueous solvent type secondary batteries of Examples 1 to 12 including both the cyclic acid anhydride and the succinimide compound, the initial discharge capacity is larger than that of Comparative Example 6 and that of Comparative Examples 1 to 3. Although the degree is the same, the high load discharge efficiency and the high temperature charge storage characteristics are almost the same as those of Comparative Example 6.
一方、ゲル状非水溶媒系電解質を使用した場合は、
（ｄ）環状酸無水物のみを含み、スクシンイミド化合物を含まない比較例７の非水溶媒系二次電池では、初回放電容量は比較例６のものよりも増大しているが、高負荷放電効率及び高温充電保存特性は比較例６のものよりも大幅に悪化している。
（ｅ）環状酸無水物及びスクシンイミド化合物の両者を含む実施例１３及び１４の非水溶媒系二次電池では、初回放電容量は比較例６のものよりも大で比較例７のものと同程度であり、高負荷放電効率は比較例６のものよりも劣るが比較例７のものよりは大幅に優れており、更に高温充電保存特性は、比較例６のものと同程度であって、比較例７のものと比すると大幅によい結果が得られている。
On the other hand, when using a gel-like nonaqueous solvent electrolyte,
(D) In the non-aqueous solvent secondary battery of Comparative Example 7 containing only the cyclic acid anhydride and no succinimide compound, the initial discharge capacity was higher than that of Comparative Example 6, but the high-load discharge efficiency was high. The high-temperature charge storage characteristics are much worse than those of Comparative Example 6.
(E) In the non-aqueous solvent type secondary batteries of Examples 13 and 14 containing both the cyclic acid anhydride and the succinimide compound, the initial discharge capacity was larger than that of Comparative Example 6 and comparable to that of Comparative Example 7. The high-load discharge efficiency is inferior to that of Comparative Example 6, but is significantly better than that of Comparative Example 7, and the high-temperature charge storage characteristics are comparable to those of Comparative Example 6, Significantly better results are obtained compared to Example 7.
以上の（ａ）〜（ｅ）の結果をまとめると、液状非水溶媒系電解質及びゲル状非水溶媒系電解質のいずれの場合であっても、
（ａ’）環状酸無水物のみを添加すると初回放電容量の改善につながるが、高負荷放電効率及び高温充電保存特性は悪化し、
（ｂ’）環状酸無水物及びスクシンイミド化合物の両者を添加すると、初回放電容量、高負荷放電効率及び高温充電保存特性共に良好な結果が得られる、
ことがわかる。
Summarizing the results of (a) to (e) above, in any case of a liquid non-aqueous solvent electrolyte and a gel non-aqueous solvent electrolyte,
(A ′) When only cyclic acid anhydride is added, the initial discharge capacity is improved, but the high load discharge efficiency and high temperature charge storage characteristics are deteriorated,
(B ′) When both a cyclic acid anhydride and a succinimide compound are added, good results are obtained in both initial discharge capacity, high load discharge efficiency and high temperature charge storage characteristics.
I understand that.
（実施例１５〜１７、参考例１〜３）
実施例１５〜１６、参考例１〜２では、前記実施例３の非水電解液二次電池と同様に、環状酸無水物として無水コハク酸を全非水溶媒系電解質質量に対して１．５質量％となるように添加し、スクシンイミド化合物としてＮ−メチルスクシンイミドの添加量を全非水溶媒系電解質質量に対して０．１〜３．０質量％まで変化させた４種類の非水溶媒系二次電池を作製した。この実施例１５〜１６、参考例１〜２の電池について前記実施例１〜１４と同様にして初回放電容量、高負荷放電効率及び高温充電保存特性を測定した。結果を実施例３の結果と共にまとめて表２に示した。
(Examples 15 to 17, Reference Examples 1 to 3 )
In Examples 15 to 16 and Reference Examples 1 and 2 , as in the case of the nonaqueous electrolyte secondary battery of Example 3, succinic anhydride was used as a cyclic acid anhydride with respect to the total nonaqueous solvent based electrolyte mass. 4 types of non-aqueous solvents which were added so as to be 5% by mass, and the addition amount of N-methylsuccinimide as a succinimide compound was changed to 0.1-3.0% by mass with respect to the total mass of the non-aqueous solvent electrolyte. A secondary battery was prepared. The batteries of Examples 15 to 16 and Reference Examples 1 to 2 were measured for initial discharge capacity, high load discharge efficiency, and high temperature charge storage characteristics in the same manner as in Examples 1 to 14. The results are shown in Table 2 together with the results of Example 3.
また、実施例１７及び参考例３の非水溶媒系二次電池では、前記実施例９の非水電解液二次電池と同様に、環状酸無水物として無水コハク酸を全非水溶媒系電解質質量に対して１．５質量％となるように添加し、スクシンイミド化合物としてＮ−エチルスクシンイミドの添加量を全非水溶媒系電解質質量に対して０．５及び２．０質量％添加して２種類の非水溶媒系二次電池を作製した。この実施例１７及び参考例３の電池について前記実施例１〜１４と同様にして初回放電容量、高負荷放電効率及び高温充電保存特性を測定した。結果を実施例９の結果と共にまとめて表２に示した。
In the nonaqueous solvent secondary battery of Example 17 and Reference Example 3, as in the nonaqueous electrolyte secondary battery of Example 9, succinic anhydride was used as the cyclic acid anhydride for the entire nonaqueous solvent electrolyte. The amount of N-ethylsuccinimide added as a succinimide compound is 0.5% by mass and 2.0% by mass with respect to the total mass of the nonaqueous solvent electrolyte. Various types of nonaqueous solvent secondary batteries were produced. The batteries of Example 17 and Reference Example 3 were measured for initial discharge capacity, high load discharge efficiency, and high temperature charge storage characteristics in the same manner as in Examples 1-14. The results are shown in Table 2 together with the results of Example 9.
表２に示した結果から、スクシンイミド化合物が０．１質量％と少ない参考例１の非水溶媒系二次電池では、実施例１５〜１７、参考例２〜３、実施例３及び９のものと比すると、高負荷放電効率及び高温充電保存特性がわずかに低下しているが、それでも環状酸無水物のみを含有している比較例１〜３のものと比すると良好な結果が得られている。スクシンイミド化合物含有量が０．５％以上の実施例１５〜１７、参考例２〜３の非水溶媒系二次電池では、初回放電容量、高負荷放電効率及び高温充電保存特性共に実施例３ないしは実施例９と同等の良好な結果が得られている。 From the results shown in Table 2, in the nonaqueous solvent type secondary battery of Reference Example 1 having a low succinimide compound of 0.1% by mass, those of Examples 15 to 17, Reference Examples 2 to 3 , and Examples 3 and 9 were used. The high load discharge efficiency and the high-temperature charge storage characteristics are slightly reduced as compared with those of Comparative Examples 1 to 3 that still contain only cyclic acid anhydrides. Yes. In the nonaqueous solvent type secondary batteries of Examples 15 to 17 and Reference Examples 2 to 3 having a succinimide compound content of 0.5% or more, Examples 3 to Good results equivalent to those of Example 9 are obtained.
このような環状酸無水物が添加されている非水溶媒系電解質に対してスクシンイミド化合物を添加したことによる高負荷放電効率及び高温充電保存特性の改善効果は、全非水溶媒系電解質質量に対して０．０１質量％程度から見られ、０．０５質量％以上で非常に良好となり、約０．５質量％以上でその効果が飽和する傾向が見られる。したがって、前記スクシンイミド化合物の含有量は、全電解質質量の０．０１質量％以上が好ましく、より好ましくは０．０５質量％以上である。前記スクシンイミド化合物の含有量は、１０質量％程度まで添加しても所定の効果を奏するが、５質量％を超えて添加すると非水溶媒系電解質のイオン伝導率が減少しだすので、上限は５質量％とすることが好ましい。 The effect of improving the high-load discharge efficiency and high-temperature charge storage characteristics due to the addition of the succinimide compound to the non-aqueous solvent electrolyte to which such cyclic acid anhydride is added is based on the total mass of the non-aqueous solvent electrolyte. From about 0.01% by mass, it becomes very good at 0.05% by mass or more, and the effect tends to be saturated at about 0.5% by mass or more. Therefore, the content of the succinimide compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total electrolyte mass. Even if the content of the succinimide compound is added up to about 10% by mass, a predetermined effect can be obtained. However, if the content exceeds 5% by mass, the ionic conductivity of the nonaqueous solvent electrolyte starts to decrease, so the upper limit is 5% by mass. % Is preferable.
なお、上述の実施例１〜１７、参考例１〜３においては、各環状酸無水物及び各スクシンイミド化合物を１種類ずつ添加した例を示したが、それぞれを複数添加しても同様の効果が生じることは当業者にとり自明であろう。
In Examples 1 to 17 and Reference Examples 1 to 3 described above, examples in which each cyclic acid anhydride and each succinimide compound were added one by one were shown. It will be apparent to those skilled in the art that this occurs.
Claims (12)
（１）環状酸無水物、及び
（２）Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種、
を含有し、
前記環状酸無水物の含有量は、全電解質質量の０．０１〜１０質量％の範囲であり、
前記Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種の含有量は、全電解質質量の０．０１〜１０質量％の範囲であり、
前記非水溶媒系電解液中の前記Ｎ−アルキルスクシンイミド化合物、Ｎ−アルケニルスクシンイミド化合物、Ｎ−アリールスクシンイミド化合物から選択された少なくとも１種と前記環状酸無水物との質量比は、１：２〜２：１の範囲である
ことを特徴とする非水溶媒系二次電池。 A non-aqueous solvent system comprising a positive electrode including a positive electrode active material capable of reversibly occluding and releasing lithium, a negative electrode including a negative electrode active material capable of reversibly occluding and releasing lithium, and a non-aqueous solvent electrolyte In the secondary battery, in the non-aqueous solvent electrolyte,
(1) cyclic acid anhydride, and (2) at least one selected from N-alkyl succinimide compounds, N-alkenyl succinimide compounds, and N-aryl succinimide compounds,
Containing
The content of the cyclic acid anhydride is in the range of 0.01 to 10% by mass of the total electrolyte mass,
The N- alkyl succinimides compound, N- alkenyl succinimide compound, N- aryl disk at least one content Shin selected from imide compounds, Ri range der of 0.01 to 10% by weight of the total electrolyte weight,
The mass ratio of the cyclic acid anhydride to at least one selected from the N-alkyl succinimide compound, N-alkenyl succinimide compound and N-aryl succinimide compound in the non-aqueous solvent electrolyte is 1: 2 A non-aqueous solvent type secondary battery characterized by being in a range of 2: 1 .
（ただし、ｎ＝０〜４の整数であり、Ｒ１〜Ｒ４は、同じであっても異なっていても良く、Ｈもしくはアルキル基、アルケニル基又はアリール基からなる炭素数１〜１２の有機基を示す。また、Ｒ１〜Ｒ４は互いに結合して環を形成していてもよい。） The non-aqueous solvent secondary battery according to claim 1, wherein the cyclic acid anhydride is represented by the following chemical formula.
(However, n is an integer of 0 to 4, and R 1 to R 4 may be the same or different, and is an organic group having 1 to 12 carbon atoms composed of H, an alkyl group, an alkenyl group, or an aryl group. And R 1 to R 4 may be bonded to each other to form a ring.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003326733A JP4707313B2 (en) | 2003-09-18 | 2003-09-18 | Non-aqueous solvent type secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003326733A JP4707313B2 (en) | 2003-09-18 | 2003-09-18 | Non-aqueous solvent type secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005093293A JP2005093293A (en) | 2005-04-07 |
| JP4707313B2 true JP4707313B2 (en) | 2011-06-22 |
Family
ID=34456830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003326733A Expired - Lifetime JP4707313B2 (en) | 2003-09-18 | 2003-09-18 | Non-aqueous solvent type secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4707313B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008123714A (en) * | 2006-11-08 | 2008-05-29 | Sony Corp | Electrolytic solution and battery |
| CA2625271A1 (en) * | 2008-03-11 | 2009-09-11 | Hydro-Quebec | Method for preparing an electrochemical cell having a gel electrolyte |
| CN102044675A (en) * | 2009-10-23 | 2011-05-04 | 深圳市比克电池有限公司 | Lithium battery anode slurry additive, slurry, battery and preparation method |
| JP5552077B2 (en) * | 2011-02-25 | 2014-07-16 | 三井化学株式会社 | Nonaqueous electrolyte containing phosphorus derivative and lithium secondary battery |
| JP5720325B2 (en) * | 2011-03-11 | 2015-05-20 | 三菱化学株式会社 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same |
| IN2014CN02844A (en) | 2011-10-17 | 2015-07-03 | Ube Industries | |
| CN113871692A (en) * | 2020-06-30 | 2021-12-31 | 东营市海科新源化工有限责任公司 | Lithium ion battery |
| CN112467212B (en) * | 2020-10-30 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte for silicon-carbon cathode and lithium ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002216848A (en) * | 2001-01-23 | 2002-08-02 | Sony Corp | Gelled electrolyte, and gelled electrolyte cell using the same |
| JP2002324580A (en) * | 2001-02-23 | 2002-11-08 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
| JP2003007333A (en) * | 2001-06-26 | 2003-01-10 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using the same |
| JP2003086248A (en) * | 2001-09-14 | 2003-03-20 | Mitsubishi Chemicals Corp | Non-aqueous electrolytic solution secondary battery and electrolytic solution |
| JP2003092137A (en) * | 2001-07-10 | 2003-03-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and secondary battery using same |
| JP2003338317A (en) * | 2002-05-17 | 2003-11-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
| JP2004071458A (en) * | 2002-08-08 | 2004-03-04 | Mitsubishi Chemicals Corp | Non-aqueous electrolytic liquid secondary battery |
| JP2004281073A (en) * | 2003-03-12 | 2004-10-07 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and battery therewith |
-
2003
- 2003-09-18 JP JP2003326733A patent/JP4707313B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002216848A (en) * | 2001-01-23 | 2002-08-02 | Sony Corp | Gelled electrolyte, and gelled electrolyte cell using the same |
| JP2002324580A (en) * | 2001-02-23 | 2002-11-08 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
| JP2003007333A (en) * | 2001-06-26 | 2003-01-10 | Mitsubishi Chemicals Corp | Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery using the same |
| JP2003092137A (en) * | 2001-07-10 | 2003-03-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and secondary battery using same |
| JP2003086248A (en) * | 2001-09-14 | 2003-03-20 | Mitsubishi Chemicals Corp | Non-aqueous electrolytic solution secondary battery and electrolytic solution |
| JP2003338317A (en) * | 2002-05-17 | 2003-11-28 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte secondary battery |
| JP2004071458A (en) * | 2002-08-08 | 2004-03-04 | Mitsubishi Chemicals Corp | Non-aqueous electrolytic liquid secondary battery |
| JP2004281073A (en) * | 2003-03-12 | 2004-10-07 | Mitsubishi Chemicals Corp | Nonaqueous electrolyte and battery therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005093293A (en) | 2005-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4748930B2 (en) | Non-aqueous solvent type secondary battery | |
| US8916297B2 (en) | Method of preparing gel polymer electrolyte secondary battery and gel polymer electrolyte secondary battery | |
| JP4992921B2 (en) | Non-aqueous electrolyte secondary battery | |
| JP2004103573A (en) | Electrolyte for lithium cell and lithium cell containing it | |
| JP5163065B2 (en) | Non-aqueous electrolyte secondary battery and non-aqueous electrolyte composition | |
| JP4014816B2 (en) | Lithium polymer secondary battery | |
| KR20080101702A (en) | Secondary battery and manufacturing method of the same | |
| JP2008112722A (en) | Lithium polymer battery | |
| JP4596763B2 (en) | Non-aqueous solvent type secondary battery | |
| KR20090084713A (en) | Non-aqueous electrolytic solution battery and non-aqueous electrolytic solution composition | |
| JP4707313B2 (en) | Non-aqueous solvent type secondary battery | |
| JP2005108515A (en) | Nonaqueous electrolyte battery | |
| JP4707312B2 (en) | Non-aqueous solvent type secondary battery | |
| JP2012248544A (en) | Lithium polymer battery | |
| JP4601273B2 (en) | Non-aqueous solvent type secondary battery | |
| KR20080029897A (en) | Polymer electrolyte secondary battery | |
| JP2005135755A (en) | Method of manufacturing carbon material for negative electrode of nonaqueous secondary battery and nonaqueous secondary battery using same | |
| JP3327468B2 (en) | Lithium ion secondary battery and method of manufacturing the same | |
| JP2001006740A (en) | Lithium secondary battery provided with polymer electrolyte, and manufacture thereof | |
| CN114142039A (en) | Binder and lithium ion battery comprising same | |
| KR100529106B1 (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising same | |
| JP2009134943A (en) | Nonaqueous electrolyte battery | |
| KR100467689B1 (en) | Organic electrolyte solution and lithium battery adopting the same | |
| JP2004200122A (en) | Manufacturing method of non-aqueous electrolyte secondary battery | |
| JP2003263984A (en) | Nonaqueous electrolyte cell and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060421 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090123 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090908 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091104 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100826 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101109 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20101206 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110215 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110315 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4707313 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| EXPY | Cancellation because of completion of term |