JP6235313B2 - Non-aqueous electrolyte and lithium ion secondary battery using the non-aqueous electrolyte - Google Patents
Non-aqueous electrolyte and lithium ion secondary battery using the non-aqueous electrolyte Download PDFInfo
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- JP6235313B2 JP6235313B2 JP2013238090A JP2013238090A JP6235313B2 JP 6235313 B2 JP6235313 B2 JP 6235313B2 JP 2013238090 A JP2013238090 A JP 2013238090A JP 2013238090 A JP2013238090 A JP 2013238090A JP 6235313 B2 JP6235313 B2 JP 6235313B2
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- phosphate
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- ethylene
- aqueous electrolyte
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 46
- -1 cyclic phosphate compound Chemical class 0.000 claims description 154
- 239000008151 electrolyte solution Substances 0.000 claims description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 229910003002 lithium salt Inorganic materials 0.000 claims description 40
- 229910019142 PO4 Inorganic materials 0.000 claims description 27
- 239000010452 phosphate Substances 0.000 claims description 27
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910013872 LiPF Inorganic materials 0.000 claims description 11
- 101150058243 Lipf gene Proteins 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910012258 LiPO Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 6
- 229910013075 LiBF Inorganic materials 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 97
- 238000012360 testing method Methods 0.000 description 78
- 230000014759 maintenance of location Effects 0.000 description 33
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 30
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 25
- 239000002904 solvent Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 22
- 229910052731 fluorine Inorganic materials 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 18
- 239000012046 mixed solvent Substances 0.000 description 18
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 18
- NNCOTENANFCLQG-UHFFFAOYSA-N 2-but-3-ynoxy-1,3,2lambda5-dioxaphospholane 2-oxide Chemical compound C(CC#C)OP1(OCCO1)=O NNCOTENANFCLQG-UHFFFAOYSA-N 0.000 description 16
- 239000007774 positive electrode material Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
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- 125000001033 ether group Chemical group 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000005678 chain carbonates Chemical class 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
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- IRTRDBVMWSUNTK-UHFFFAOYSA-N 2-hydroxy-4-(2,2,2-trifluoroethyl)-1,3,2lambda5-dioxaphospholane 2-oxide Chemical compound OP1(=O)OCC(CC(F)(F)F)O1 IRTRDBVMWSUNTK-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
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- 230000005611 electricity Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
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- PBKCJVXMBQUKBQ-UHFFFAOYSA-N 2-octoxy-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound CCCCCCCCOP1(=O)OCCO1 PBKCJVXMBQUKBQ-UHFFFAOYSA-N 0.000 description 3
- RJKGEFYRXRRZKT-UHFFFAOYSA-N 2-prop-2-ynoxy-1,3,2lambda5-dioxaphospholane 2-oxide Chemical compound P1(=O)(OCC#C)OCCO1 RJKGEFYRXRRZKT-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- NYGFLHQWSWRNIP-UHFFFAOYSA-N 2-(2,2,2-trifluoroethoxy)-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound FC(F)(F)COP1(=O)OCCO1 NYGFLHQWSWRNIP-UHFFFAOYSA-N 0.000 description 2
- WMPINAVYCPYNDG-UHFFFAOYSA-N 2-but-2-enoxy-4-methyl-1,3,2lambda5-dioxaphospholane 2-oxide Chemical compound P1(=O)(OCC(C)O1)OCC=CC WMPINAVYCPYNDG-UHFFFAOYSA-N 0.000 description 2
- VZTHENWFXHTQDZ-UHFFFAOYSA-N 2-hexoxy-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound CCCCCCOP1(=O)OCCO1 VZTHENWFXHTQDZ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
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- 239000011331 needle coke Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006611 nonyloxy group Chemical group 0.000 description 1
- 125000005071 nonynyl group Chemical group C(#CCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Description
本発明は、非水電解液及び当該非水電解液を用いたリチウムイオン二次電池に関する。 The present invention relates to a non-aqueous electrolyte and a lithium ion secondary battery using the non-aqueous electrolyte.
リチウムイオン二次電池は、高エネルギー密度、高耐久性といった優れた特徴を持つことから、携帯電話などのモバイル電子機器用電源として汎用されており、近年では電気自動車などの自動車用電源としても利用されている。 Lithium ion secondary batteries are widely used as power sources for mobile electronic devices such as mobile phones because they have excellent characteristics such as high energy density and high durability. In recent years, they are also used as power sources for automobiles such as electric vehicles. Has been.
現状において、リチウムイオン二次電池は広く普及しているが、モバイル電子機器や電気自動車のユーザーからは、依然として電池の高エネルギー密度化の要請がある。これに応えるべく、電池のエネルギー密度を向上させる試みが活発になされており、中でも、正極活物質の充電深度の拡大や高電位正極の開発が注目されている。特許文献1によると、リチウム−コバルト複合酸化物(LiCoO2)は、正極電位がリチウム基準4.3Vになるまで充電すると、充電容量が約155mAh/gであるのに対して、4.5Vになるまで充電すると、充電容量が190mAh/g以上となる。このように、満充電時の正極の電位を引き上げることで、正極活物質の利用率が向上し、結果として電池のエネルギー密度を高めることができる。 At present, lithium ion secondary batteries are widely used. However, users of mobile electronic devices and electric vehicles still have a demand for higher energy density of batteries. In order to respond to this, attempts to improve the energy density of the battery are actively made, and in particular, attention has been paid to the expansion of the charging depth of the positive electrode active material and the development of a high potential positive electrode. According to Patent Document 1, when the lithium-cobalt composite oxide (LiCoO 2 ) is charged until the positive electrode potential becomes 4.3 V of lithium reference, the charging capacity is about 155 mAh / g, whereas it is 4.5 V. When it is charged until it becomes, the charge capacity becomes 190 mAh / g or more. Thus, by raising the potential of the positive electrode during full charge, the utilization factor of the positive electrode active material is improved, and as a result, the energy density of the battery can be increased.
ところで、リチウムイオン二次電池では、非水溶媒にリチウム電解質を溶解させた非水電解液を用いている。非水溶媒としては、エチレンカーボネート、プロピレンカーボネートなどの環状カーボネート類と、ジメチルカーボネート、エチルメチルカーボネートなどの鎖状カーボネート類とを、特定の比率で混合してなるカーボネート溶媒が採用されている。カーボネート溶媒は、満充電時の正極電位がリチウム基準で4.3V程度の従来のリチウムイオン二次電池に適用した場合は、十分な耐酸化性及び耐還元性を併せ持ち、リチウムイオン伝導性にも優れることから、汎用されるに至った。しかしながら、従来よりも正極電位が高い電池においては、カーボネート溶媒が分解してしまうため、分解物の堆積や電池内部でのガス発生が起こり、サイクル特性などの電池特性が低下するという問題が生じる。 By the way, in the lithium ion secondary battery, a nonaqueous electrolytic solution in which a lithium electrolyte is dissolved in a nonaqueous solvent is used. As the non-aqueous solvent, a carbonate solvent obtained by mixing cyclic carbonates such as ethylene carbonate and propylene carbonate and chain carbonates such as dimethyl carbonate and ethyl methyl carbonate in a specific ratio is employed. Carbonate solvent has sufficient oxidation resistance and reduction resistance when applied to a conventional lithium ion secondary battery having a positive electrode potential of about 4.3 V with respect to lithium when fully charged, and also has lithium ion conductivity. Due to its superiority, it has been widely used. However, in a battery having a higher positive electrode potential than the conventional battery, since the carbonate solvent is decomposed, deposition of decomposition products and gas generation inside the battery occur, resulting in a problem that battery characteristics such as cycle characteristics deteriorate.
上記の問題を解決するために、特許文献2では、非水溶媒として、フッ素化された非水溶媒を使用し、非水電解液の耐酸化性を向上させる方法が提案されている。具体的には、フッ素化エステル及びフッ素化エーテルを合計50体積%と高濃度で用いることにより、電解液の耐酸化性向上を図っている。 In order to solve the above problem, Patent Document 2 proposes a method for improving the oxidation resistance of a nonaqueous electrolytic solution by using a fluorinated nonaqueous solvent as a nonaqueous solvent. Specifically, the oxidation resistance of the electrolytic solution is improved by using fluorinated ester and fluorinated ether at a high concentration of 50% by volume in total.
また、特許文献3、4では、非水電解液中に、特定の環状リン酸エステルを含有させることで、電池のサイクル性能、保存性能を向上させる方法が提案されている。具体的には、特許文献3では、含フッ素環状リン酸エステルとして2,2,2−トリフルオロエチルエチレンフォスフェートを、非水溶媒に対して15体積%含有させることにより、サイクル特性の向上を図っている。また、特許文献4では、環状リン酸エステルとして2−メトキシ−1,3,2−フォスフォラン−2−オキサイドを非水溶媒に対して50体積%と高濃度で用いることで、電池の高温保存時の自己放電の抑制を図っている。 Patent Documents 3 and 4 propose a method for improving the cycle performance and storage performance of a battery by including a specific cyclic phosphate in the nonaqueous electrolytic solution. Specifically, in Patent Document 3, the cycle characteristics are improved by containing 15% by volume of 2,2,2-trifluoroethylethylene phosphate as a fluorine-containing cyclic phosphate ester with respect to the non-aqueous solvent. I am trying. In Patent Document 4, 2-methoxy-1,3,2-phosphorane-2-oxide is used as a cyclic phosphate ester at a high concentration of 50% by volume with respect to the nonaqueous solvent, so that the battery can be stored at high temperature. The self-discharge at the time is suppressed.
しかしながら、特許文献2に開示されているフッ素化された非水溶媒を用いる場合、非水溶媒へのリチウム電解質の溶解性が低下すると共に、電解液のイオン伝導性が大幅に低下する。これにより、電池の入出力特性が低下し、また、電池の入出力特性が低下した結果、サイクル特性が低下する恐れがある。 However, when the fluorinated nonaqueous solvent disclosed in Patent Document 2 is used, the solubility of the lithium electrolyte in the nonaqueous solvent is lowered, and the ionic conductivity of the electrolytic solution is greatly lowered. As a result, the input / output characteristics of the battery are degraded, and as a result of the degradation of the input / output characteristics of the battery, the cycle characteristics may be degraded.
また、特許文献3に開示されている2,2,2−トリフルオロエチルエチレンフォスフェートを非水溶媒に対して15質量%非水電解液に含有させる場合、あるいは特許文献4に開示されている2−メトキシ−1,3,2−フォスフォラン−2−オキサイドを非水溶媒に対して50体積%非水電解液に含有させる場合、従来よりも高い正極電位を有するリチウムイオン二次電池において、ガスの発生抑制や、サイクル特性を向上させる効果は十分とは言えない。 Further, when 2,2,2-trifluoroethylethylene phosphate disclosed in Patent Document 3 is contained in a 15% by mass non-aqueous electrolyte with respect to the non-aqueous solvent, or disclosed in Patent Document 4. In the case where 2-methoxy-1,3,2-phosphorane-2-oxide is contained in a 50% by volume non-aqueous electrolyte with respect to the non-aqueous solvent, in a lithium ion secondary battery having a higher positive electrode potential than in the past, The effects of suppressing gas generation and improving cycle characteristics are not sufficient.
上述のように、従来技術では、高い正極電位を有するリチウムイオン二次電池において、サイクル劣化やガス発生を十分に抑制する解決策は示されていない。 As described above, the conventional technology does not show a solution for sufficiently suppressing cycle deterioration and gas generation in a lithium ion secondary battery having a high positive electrode potential.
本発明は、上記した課題に鑑みてなされたものであり、従来よりも高い正極電位を有するリチウムイオン二次電池に適用した場合でもガスの発生、すなわち電解液の分解が抑制され、サイクル特性に優れるリチウムイオン二次電池を与える非水電解液及び当該非水電解液を用いたリチウムイオン二次電池を提供することを目的とする。 The present invention has been made in view of the above-described problems, and even when applied to a lithium ion secondary battery having a higher positive electrode potential than the conventional one, generation of gas, that is, decomposition of the electrolyte is suppressed, and cycle characteristics are improved. An object of the present invention is to provide a non-aqueous electrolyte solution that provides an excellent lithium-ion secondary battery and a lithium-ion secondary battery using the non-aqueous electrolyte solution.
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、非水溶媒中に、特定の環状リン酸エステル化合物(A)と、シュウ酸構造を有さないリチウム塩化合物(B)と、シュウ酸構造を有するリチウム塩化合物(C)とをそれぞれ一種以上含有する非水電解液を用いることで、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention have obtained a specific cyclic phosphate compound (A) and a lithium salt compound (B) having no oxalic acid structure in a non-aqueous solvent. And it discovered that the said subject could be solved by using the nonaqueous electrolyte solution which each contains 1 or more types of lithium salt compounds (C) which have an oxalic acid structure, and came to complete this invention.
即ち、本発明は下記の通りである。
〔1〕
下記一般式(1)で表される環状リン酸エステル化合物(A)と、
シュウ酸構造を有さないリチウム塩化合物(B)と、
シュウ酸構造を有するリチウム塩化合物(C)と、
非水溶媒と、を含有し、
前記環状リン酸エステル化合物(A)の含有量が、前記非水電解液の総量に対して、0.01質量%以上10質量%以下である、非水電解液。
〔2〕
前記リチウム塩化合物(B)の含有量が、前記非水電解液の総量に対して、3質量%以上30質量%以下であり、
前記リチウム塩化合物(C)の含有量が、前記非水電解液の総量に対して、0.01質量%以上10質量%以下である、前項〔1〕に記載の非水電解液。
〔3〕
前記リチウム塩化合物(B)が、LiPF6を含む、前項〔1〕又は〔2〕に記載の非水電解液。
〔4〕
前記リチウム塩化合物(B)が、LiPF6と、LiPO2F2及び/又はLiBF4と、を含む、前項〔1〕〜〔3〕のいずれか一項に記載の非水電解液。
〔5〕
前記リチウム塩化合物(C)が、LiB(C2O4)2、LiBF2(C2O4)、LiP(C2O4)3、LiPF2(C2O4)2及びLiPF4(C2O4)からなる群より選ばれる一種以上のリチウム塩化合物を含む、前項〔1〕〜〔4〕のいずれか一項に記載の非水電解液。
〔6〕
前記環状リン酸エステル化合物(A)が、前記一般式(1)におけるR2がエチレン基又はプロピレン基である環状リン酸エステル化合物を含む、前項〔1〕〜〔5〕のいずれか一項に記載の非水電解液。
〔7〕
正極と、負極と、前項〔1〕〜〔6〕のいずれか一項に記載の非水電解液と、を備え、満充電時の前記正極の電位が、リチウム基準で4.4V以上5.5V以下である、リチウムイオン二次電池。
That is, the present invention is as follows.
[1]
A cyclic phosphate compound (A) represented by the following general formula (1);
A lithium salt compound (B) having no oxalic acid structure;
A lithium salt compound (C) having an oxalic acid structure;
A non-aqueous solvent ,
A nonaqueous electrolytic solution in which the content of the cyclic phosphate compound (A) is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the nonaqueous electrolytic solution.
[2]
The content of the lithium salt compound (B) is 3% by mass or more and 30% by mass or less with respect to the total amount of the non-aqueous electrolyte,
The nonaqueous electrolytic solution according to [1] , wherein the content of the lithium salt compound (C) is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the nonaqueous electrolytic solution.
[3]
The nonaqueous electrolytic solution according to [1] or [2] , wherein the lithium salt compound (B) contains LiPF 6 .
[4]
The nonaqueous electrolytic solution according to any one of [1] to [3] , wherein the lithium salt compound (B) includes LiPF 6 and LiPO 2 F 2 and / or LiBF 4 .
[5]
The lithium salt compound (C) is LiB (C 2 O 4 ) 2 , LiBF 2 (C 2 O 4 ), LiP (C 2 O 4 ) 3 , LiPF 2 (C 2 O 4 ) 2 and LiPF 4 (C 2. The nonaqueous electrolytic solution according to any one of [1] to [4] above, which contains one or more lithium salt compounds selected from the group consisting of 2 O 4 ).
[6]
In any one of [1] to [5] , the cyclic phosphate compound (A) includes a cyclic phosphate compound in which R 2 in the general formula (1) is an ethylene group or a propylene group. The non-aqueous electrolyte described.
[7]
4. A positive electrode, a negative electrode, and the non-aqueous electrolyte solution according to any one of [1] to [6] above, wherein the potential of the positive electrode when fully charged is 4.4 V or more based on lithium. A lithium ion secondary battery having a voltage of 5 V or less.
本発明によれば、従来よりも高い正極電位を有するリチウムイオン二次電池に適用した場合でもガスの発生、すなわち電解液の分解が抑制され、サイクル特性に優れるリチウムイオン二次電池を与える非水電解液及び当該非水電解液を用いたリチウムイオン二次電池を提供することができる。 According to the present invention, even when applied to a lithium ion secondary battery having a higher positive electrode potential than the conventional one, the generation of gas, that is, the decomposition of the electrolytic solution is suppressed, and a non-aqueous battery that provides a lithium ion secondary battery having excellent cycle characteristics is provided. A lithium ion secondary battery using the electrolytic solution and the non-aqueous electrolytic solution can be provided.
以下、本発明を実施するための形態(以下、「本実施形態」という。)について詳細に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。 DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.
〔非水電解液〕
本実施形態の非水電解液は、下記一般式(1)で表される環状リン酸エステル化合物(A)と、シュウ酸構造を有さないリチウム塩化合物(B)と、シュウ酸構造を有するリチウム塩化合物(C)と、非水溶媒と、を含有する。これにより、本実施形態の非水電解液は、従来よりも高い正極電位を有するリチウムイオン二次電池に適用した場合でも、ガスの発生、すなわち電解液の分解が抑制される上、優れたサイクル特性を発現することができる。
The nonaqueous electrolytic solution of the present embodiment has a cyclic phosphate compound (A) represented by the following general formula (1), a lithium salt compound (B) having no oxalic acid structure, and an oxalic acid structure. A lithium salt compound (C) and a non-aqueous solvent are contained. As a result, the nonaqueous electrolytic solution of the present embodiment suppresses gas generation, that is, decomposition of the electrolytic solution, even when applied to a lithium ion secondary battery having a higher positive electrode potential than the conventional one, and an excellent cycle. Characteristic can be expressed.
〔環状リン酸エステル化合物(A)〕
本実施形態において、一般式(1)中、R1は、ヒドロキシ基、置換されていてもよい炭素数1以上15以下のアルコキシ基、置換されていてもよい炭素数1以上15以下のアルキル基、置換されていてもよい炭素数2以上15以下のアルケニル基、置換されていてもよい炭素数2以上15以下のアルキニル基、及び置換されていてもよい炭素数6以上15以下のアリール基からなる群より選ばれる一種の基を表す。
[Cyclic phosphate ester compound (A)]
In the present embodiment, in general formula (1), R 1 is a hydroxy group, an optionally substituted alkoxy group having 1 to 15 carbon atoms, or an optionally substituted alkyl group having 1 to 15 carbon atoms. An alkenyl group having 2 to 15 carbon atoms which may be substituted, an alkynyl group having 2 to 15 carbon atoms which may be substituted, and an aryl group having 6 to 15 carbon atoms which may be substituted Represents a kind of group selected from the group consisting of
上記アルコキシ基としては、特に限定されないが、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチロキシ基、ヘキシロキシ基、ヘプチロキシ基、オクチロキシ基、ノニロキシ基、デシロキシ基などが挙げられる。これらのアルコキシ基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。また、上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、フェニル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。これらの中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アルコキシ基の炭素数としては、ガス発生抑制の観点から、1以上15以下であり、好ましくは1以上10以下であり、より好ましくは1以上8以下であり、さらに好ましくは2以上6以下である。 The alkoxy group is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group. The hydrogen atom or carbon atom of these alkoxy groups may be substituted with a different element or a substituent as necessary. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. The substituent is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a phenyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group. , Ether groups, sulfide groups, carbonyl groups, and sulfonyl groups. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The number of carbon atoms of the alkoxy group is 1 or more and 15 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and further preferably 2 or more and 6 or less, from the viewpoint of suppressing gas generation. is there.
次に、上記アルキル基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基が挙げられる。これらのアルキル基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、フェニル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。これらの中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アルキル基の炭素数としては、ガス発生抑制の観点から、1以上15以下であり、好ましくは1以上10以下であり、より好ましくは1以上8以下であり、さらに好ましくは2以上6以下である。 Next, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The hydrogen atom or carbon atom of these alkyl groups may be substituted with a different element or a substituent as necessary. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. The substituent is not particularly limited. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, cyano group, nitro group, hydroxy group, carboxy group, sulfo group, phosphono group, ether Groups, sulfide groups, carbonyl groups and sulfonyl groups. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The number of carbon atoms of the alkyl group is 1 or more and 15 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and further preferably 2 or more and 6 or less from the viewpoint of suppressing gas generation. is there.
また、上記アルケニル基としては、特に限定されないが、例えば、エテニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基が挙げられる。これらのアルケニル基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、フェニル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。これらの中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アルケニル基の炭素数としては、ガス発生抑制の観点から、2以上15以下であり、好ましくは2以上10以下であり、より好ましくは2以上8以下であり、さらに好ましくは2以上6以下である。 The alkenyl group is not particularly limited, and examples thereof include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group. The hydrogen atom or carbon atom of these alkenyl groups may be substituted with a different element or a substituent, if necessary. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. The substituent is not particularly limited. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, cyano group, nitro group, hydroxy group, carboxy group, sulfo group, phosphono group, ether Groups, sulfide groups, carbonyl groups and sulfonyl groups. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The carbon number of the alkenyl group is 2 or more and 15 or less, preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and further preferably 2 or more and 6 or less, from the viewpoint of suppressing gas generation. is there.
また、上記アルキニル基としては、特に限定されないが、例えば、エチニル基、プロピニル基、ブチニル基、ペンチニル基、ヘキシニル基、ヘプチニル基、オクチニル基、ノニニル基、デシニル基が挙げられる。これらのアルキニル基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、フェニル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。これらの中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アルキニル基の炭素数としては、ガス発生抑制の観点から、2以上15以下であり、好ましくは2以上10以下であり、より好ましくは2以上8以下であり、さらに好ましくは2以上6以下である。 The alkynyl group is not particularly limited, and examples thereof include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, and a decynyl group. The hydrogen atom or carbon atom of these alkynyl groups may be substituted with a different element or a substituent as needed. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. The substituent is not particularly limited. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, cyano group, nitro group, hydroxy group, carboxy group, sulfo group, phosphono group, ether Groups, sulfide groups, carbonyl groups and sulfonyl groups. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The number of carbon atoms of the alkynyl group is 2 or more and 15 or less, preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and further preferably 2 or more and 6 or less, from the viewpoint of suppressing gas generation. is there.
上記アリール基としては、特に限定されないが、例えば、フェニル基、1−ナフチル基、2−ナフチル基、ベンジル基などが挙げられる。これらのアリール基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。この中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アリール基の炭素数としては、ガス発生抑制の観点から、6以上15以下であり、好ましくは6以上10以下であり、より好ましくは6以上8以下であり、さらに好ましくは6以上7以下である。 Although it does not specifically limit as said aryl group, For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, a benzyl group etc. are mentioned. The hydrogen atom or carbon atom of these aryl groups may be substituted with a different element or a substituent, if necessary. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. Examples of the substituent include, but are not limited to, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyano group, nitro group, hydroxy group, carboxy group, sulfo group, phosphono group, ether group, sulfide. A group, a carbonyl group, and a sulfonyl group. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The number of carbon atoms of the aryl group is 6 or more and 15 or less, preferably 6 or more and 10 or less, more preferably 6 or more and 8 or less, and further preferably 6 or more and 7 or less, from the viewpoint of suppressing gas generation. is there.
R1としては、特に限定されないが、サイクル特性向上の観点から、好ましくは、ヒドロキシ基、置換されていてもよい炭素数1以上10以下のアルコキシ基、置換されていてもよい炭素数1以上10以下のアルキル基、置換されていてもよい炭素数2以上10以下のアルケニル基、置換されていてもよい炭素数2以上10以下のアルキニル基、及び置換されていてもよい炭素数6以上10以下のアリール基からなる群より選ばれる一種の基であり、より好ましくは、ヒドロキシ基、置換されていてもよい炭素数1以上8以下のアルコキシ基、置換されていてもよい炭素数1以上8以下のアルキル基、置換されていてもよい炭素数2以上8以下のアルケニル基、置換されていてもよい炭素数2以上8以下のアルキニル基、及び置換されていてもよい炭素数6以上8以下のアリール基からなる群より選ばれる一種の基であり、さらに好ましくは、ヒドロキシ基、炭素数2以上6以下のアルコキシ基、炭素数2以上6以下のアルキル基、炭素数2以上6以下のアルケニル基、炭素数2以上6以下のアルキニル基、及び炭素数6以上7以下のアリール基からなる群より選ばれる一種である。 R 1 is not particularly limited, but is preferably a hydroxy group, an optionally substituted alkoxy group having 1 to 10 carbon atoms, or an optionally substituted carbon number of 1 to 10 from the viewpoint of improving cycle characteristics. The following alkyl groups, optionally substituted alkenyl groups having 2 to 10 carbon atoms, optionally substituted alkynyl groups having 2 to 10 carbon atoms, and optionally substituted 6 to 10 carbon atoms A group selected from the group consisting of aryl groups, more preferably a hydroxy group, an optionally substituted alkoxy group having 1 to 8 carbon atoms, and an optionally substituted carbon group having 1 to 8 carbon atoms. An alkyl group having 2 to 8 carbon atoms which may be substituted, an alkynyl group having 2 to 8 carbon atoms which may be substituted, and A group selected from the group consisting of aryl groups having 6 to 8 carbon atoms, more preferably a hydroxy group, an alkoxy group having 2 to 6 carbon atoms, an alkyl group having 2 to 6 carbon atoms, It is a kind selected from the group consisting of an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 7 carbon atoms.
本実施形態において、一般式(1)中のR2は、置換されていてもよい炭素数1以上10以下のアルキレン基を表す。上記アルキレン基としては、特に限定されないが、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基などを挙げることができる。これらのアルキレン基の水素原子又は炭素原子は、必要に応じて、異種元素や置換基によって置換されていてもよい。上記異種元素としては、特に限定されないが、例えば、ホウ素、ケイ素、窒素、硫黄、フッ素、塩素、臭素を挙げることができる。上記置換基としては、特に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、フェニル基、シアノ基、ニトロ基、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基、エーテル基、スルフィド基、カルボニル基、スルホニル基を挙げることができる。この中でも、ガス発生をより効果的に抑制する観点から、フッ素原子、ヒドロキシ基、カルボキシ基、スルホ基、ホスホノ基が好ましく、フッ素原子、カルボキシ基、ホスホノ基がより好ましい。上記アルキレン基の炭素数としては、ガス発生抑制の観点から、1以上10以下であり、好ましくは1以上8以下であり、より好ましくは1以上5以下、さらに好ましくは2以上3以下である。 In this embodiment, R 2 in the general formula (1) represents an optionally substituted alkylene group having 1 to 10 carbon atoms. Although it does not specifically limit as said alkylene group, For example, a methylene group, ethylene group, a propylene group, a butylene group, a pentylene group etc. can be mentioned. The hydrogen atom or carbon atom of these alkylene groups may be substituted with a different element or a substituent as needed. Although it does not specifically limit as said dissimilar element, For example, boron, silicon, nitrogen, sulfur, a fluorine, chlorine, a bromine can be mentioned. The substituent is not particularly limited. For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, phenyl group, cyano group, nitro group, hydroxy group, carboxy group, sulfo group, phosphono group, ether Groups, sulfide groups, carbonyl groups and sulfonyl groups. Among these, from the viewpoint of more effectively suppressing gas generation, a fluorine atom, a hydroxy group, a carboxy group, a sulfo group, and a phosphono group are preferable, and a fluorine atom, a carboxy group, and a phosphono group are more preferable. The number of carbon atoms of the alkylene group is 1 or more and 10 or less, preferably 1 or more and 8 or less, more preferably 1 or more and 5 or less, and further preferably 2 or more and 3 or less from the viewpoint of suppressing gas generation.
R2としては、ガス発生をより効果的に抑制する観点から、置換されていてもよい炭素数1以上5以下のアルキレン基が好ましく、置換されていてもよい炭素数2以上3以下のアルキレン基がより好ましく、エチレン基又はプロピレン基がさらに好ましい。 R 2 is preferably an alkylene group having 1 to 5 carbon atoms which may be substituted from the viewpoint of more effectively suppressing gas generation, and may be an alkylene group having 2 to 3 carbon atoms which may be substituted. Is more preferable, and an ethylene group or a propylene group is more preferable.
本実施形態において、環状リン酸エステル化合物(A)の含有量は、より効果的にガス発生を抑制する観点から、非水電解液の総量に対して、好ましくは0.01質量%以上であり、より好ましくは0.1質量%以上であり、さらに好ましくは0.3質量%以上である。また、入出力特性の観点から、環状リン酸エステル化合物(A)の含有量は、非水電解液の総量に対して、好ましくは10質量%以下であり、より好ましくは5質量%以下であり、さらに好ましくは3質量%以下である。 In the present embodiment, the content of the cyclic phosphate compound (A) is preferably 0.01% by mass or more based on the total amount of the nonaqueous electrolytic solution from the viewpoint of more effectively suppressing gas generation. More preferably, it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more. From the viewpoint of input / output characteristics, the content of the cyclic phosphate ester compound (A) is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to the total amount of the non-aqueous electrolyte. More preferably, it is 3% by mass or less.
本実施形態における一般式(1)で表される環状リン酸エステル化合物(A)としては、特に限定されないが、例えば、メチレンメチルホスホネート、メチレンエチルホスホネート、メチレンプロピルホスホネート、メチレンブチルホスホネート、メチレンペンチルホスホネート、メチレンヘキシルホスホネート、メチレンヘプチルホスホネート、メチレンオクチルホスホネート、メチレンエテニルホスホネート、メチレン(1−プロペニル)ホスホネート、メチレン(2−プロペニル)ホスホネート、メチレン(1−ブテニル)ホスホネート、メチレン(2−ブテニル)ホスホネート、メチレン(3−ブテニル)ホスホネート、メチレン(1−ペンテニル)ホスホネート、メチレン(2−ペンテニル)ホスホネート、メチレン(3−ペンテニル)ホスホネート、メチレン(4−ペンテニル)ホスホネート、メチレンエチニルホスホネート、メチレン(1−プロピニル)ホスホネート、メチレン(2−プロピニル)ホスホネート、メチレン(1−ブチニル)ホスホネート、メチレン(2−ブチニル)ホスホネート、メチレン(3−ブチニル)ホスホネート、メチレン(1−ペンチニル)ホスホネート、メチレン(2−ペンチニル)ホスホネート、メチレン(3−ペンチニル)ホスホネート、メチレン(4−ペンチニル)ホスホネート、メチレンフェニルホスホネート、メチレンベンジルホスホネート、エチレンメチルホスホネート、エチレンエチルホスホネート、エチレンプロピルホスホネート、エチレンブチルホスホネート、エチレンペンチルホスホネート、エチレンヘキシルホスホネート、エチレンヘプチルホスホネート、エチレンオクチルホスホネート、エチレンエテニルホスホネート、エチレン(1−プロペニル)ホスホネート、エチレン(2−プロペニル)ホスホネート、エチレン(1−ブテニル)ホスホネート、エチレン(2−ブテニル)ホスホネート、エチレン(3−ブテニル)ホスホネート、エチレン(1−ペンテニル)ホスホネート、エチレン(2−ペンテニル)ホスホネート、エチレン(3−ペンテニル)ホスホネート、エチレン(4−ペンテニル)ホスホネート、エチレンエチニルホスホネート、エチレン(1−プロピニル)ホスホネート、エチレン(2−プロピニル)ホスホネート、エチレン(1−ブチニル)ホスホネート、エチレン(2−ブチニル)ホスホネート、エチレン(3−ブチニル)ホスホネート、エチレン(1−ペンチニル)ホスホネート、エチレン(2−ペンチニル)ホスホネート、エチレン(3−ペンチニル)ホスホネート、エチレン(4−ペンチニル)ホスホネート、エチレンフェニルホスホネート、エチレンベンジルホスホネート、プロピレンメチルホスホネート、プロピレンエチルホスホネート、プロピレンプロピルホスホネート、プロピレンブチルホスホネート、プロピレンペンチルホスホネート、プロピレンヘキシルホスホネート、プロピレンヘプチルホスホネート、プロピレンオクチルホスホネート、プロピレンエテニルホスホネート、プロピレン(1−プロペニル)ホスホネート、プロピレン(2−プロペニル)ホスホネート、プロピレン(1−ブテニル)ホスホネート、プロピレン(2−ブテニル)ホスホネート、プロピレン(3−ブテニル)ホスホネート、プロピレン(1−ペンテニル)ホスホネート、プロピレン(2−ペンテニル)ホスホネート、プロピレン(3−ペンテニル)ホスホネート、プロピレン(4−ペンテニル)ホスホネート、プロピレンエチニルホスホネート、プロピレン(1−プロピニル)ホスホネート、プロピレン(2−プロピニル)ホスホネート、プロピレン(1−ブチニル)ホスホネート、プロピレン(2−ブチニル)ホスホネート、プロピレン(3−ブチニル)ホスホネート、プロピレン(1−ペンチニル)ホスホネート、プロピレン(2−ペンチニル)ホスホネート、プロピレン(3−ペンチニル)ホスホネート、プロピレン(4−ペンチニル)ホスホネート、プロピレンフェニルホスホネート、プロピレンベンジルホスホネート、メチレンメチルフォスフェート、メチレンエチルフォスフェート、メチレンプロピルフォスフェート、メチレンブチルフォスフェート、メチレンペンチルフォスフェート、メチレンヘキシルフォスフェート、メチレンヘプチルフォスフェート、メチレンオクチルフォスフェート、メチレンエテニルフォスフェート、メチレン(1−プロペニル)フォスフェート、メチレン(2−プロペニル)フォスフェート、メチレン(1−ブテニル)フォスフェート、メチレン(2−ブテニル)フォスフェート、メチレン(3−ブテニル)フォスフェート、メチレン(1−ペンテニル)フォスフェート、メチレン(2−ペンテニル)フォスフェート、メチレン(3−ペンテニル)フォスフェート、メチレン(4−ペンテニル)フォスフェート、メチレンエチニルフォスフェート、メチレン(1−プロピニル)フォスフェート、メチレン(2−プロピニル)フォスフェート、メチレン(1−ブチニル)フォスフェート、メチレン(2−ブチニル)フォスフェート、メチレン(3−ブチニル)フォスフェート、メチレン(1−ペンチニル)フォスフェート、メチレン(2−ペンチニル)フォスフェート、メチレン(3−ペンチニル)フォスフェート、メチレン(4−ペンチニル)フォスフェート、メチレンフェニルフォスフェート、メチレンベンジルフォスフェート、エチレンメチルフォスフェート、エチレンエチルフォスフェート、エチレンプロピルフォスフェート、エチレンブチルフォスフェート、エチレンペンチルフォスフェート、エチレンヘキシルフォスフェート、エチレンヘプチルフォスフェート、エチレンオクチルフォスフェート、エチレンエテニルフォスフェート、エチレン(1−プロペニル)フォスフェート、エチレン(2−プロペニル)フォスフェート、エチレン(1−ブテニル)フォスフェート、エチレン(2−ブテニル)フォスフェート、エチレン(3−ブテニル)フォスフェート、エチレン(1−ペンテニル)フォスフェート、エチレン(2−ペンテニル)フォスフェート、エチレン(3−ペンテニル)フォスフェート、エチレン(4−ペンテニル)フォスフェート、エチレンエチニルフォスフェート、エチレン(1−プロピニル)フォスフェート、エチレン(2−プロピニル)フォスフェート、エチレン(1−ブチニル)フォスフェート、エチレン(2−ブチニル)フォスフェート、エチレン(3−ブチニル)フォスフェート、エチレン(1−ペンチニル)フォスフェート、エチレン(2−ペンチニル)フォスフェート、エチレン(3−ペンチニル)フォスフェート、エチレン(4−ペンチニル)フォスフェート、エチレンフェニルフォスフェート、エチレンベンジルフォスフェート、プロピレンメチルフォスフェート、プロピレンエチルフォスフェート、プロピレンプロピルフォスフェート、プロピレンブチルフォスフェート、プロピレンペンチルフォスフェート、プロピレンヘキシルフォスフェート、プロピレンヘプチルフォスフェート、プロピレンオクチルフォスフェート、プロピレンエテニルフォスフェート、プロピレン(1−プロペニル)フォスフェート、プロピレン(2−プロペニル)フォスフェート、プロピレン(1−ブテニル)フォスフェート、プロピレン(2−ブテニル)フォスフェート、プロピレン(3−ブテニル)フォスフェート、プロピレン(1−ペンテニル)フォスフェート、プロピレン(2−ペンテニル)フォスフェート、プロピレン(3−ペンテニル)フォスフェート、プロピレン(4−ペンテニル)フォスフェート、プロピレンエチニルフォスフェート、プロピレン(1−プロピニル)フォスフェート、プロピレン(2−プロピニル)フォスフェート、プロピレン(1−ブチニル)フォスフェート、プロピレン(2−ブチニル)フォスフェート、プロピレン(3−ブチニル)フォスフェート、プロピレン(1−ペンチニル)フォスフェート、プロピレン(2−ペンチニル)フォスフェート、プロピレン(3−ペンチニル)フォスフェート、プロピレン(4−ペンチニル)フォスフェート、プロピレンフェニルフォスフェート、プロピレンベンジルフォスフェートが挙げられる。 Although it does not specifically limit as cyclic phosphate ester compound (A) represented by General formula (1) in this embodiment, For example, a methylene methyl phosphonate, a methylene ethyl phosphonate, a methylene propyl phosphonate, a methylene butyl phosphonate, a methylene pentyl phosphonate Methylene hexyl phosphonate, methylene heptyl phosphonate, methylene octyl phosphonate, methylene ethenyl phosphonate, methylene (1-propenyl) phosphonate, methylene (2-propenyl) phosphonate, methylene (1-butenyl) phosphonate, methylene (2-butenyl) phosphonate, Methylene (3-butenyl) phosphonate, methylene (1-pentenyl) phosphonate, methylene (2-pentenyl) phosphonate, methylene (3-pentene Phosphonate, methylene (4-pentenyl) phosphonate, methylene ethynyl phosphonate, methylene (1-propynyl) phosphonate, methylene (2-propynyl) phosphonate, methylene (1-butynyl) phosphonate, methylene (2-butynyl) phosphonate, methylene ( 3-butynyl) phosphonate, methylene (1-pentynyl) phosphonate, methylene (2-pentynyl) phosphonate, methylene (3-pentynyl) phosphonate, methylene (4-pentynyl) phosphonate, methylene phenyl phosphonate, methylene benzyl phosphonate, ethylene methyl phosphonate, Ethylene ethyl phosphonate, ethylene propyl phosphonate, ethylene butyl phosphonate, ethylene pentyl phosphonate, ethylene hexyl phosphate Phonate, ethylene heptyl phosphonate, ethylene octyl phosphonate, ethylene ethenyl phosphonate, ethylene (1-propenyl) phosphonate, ethylene (2-propenyl) phosphonate, ethylene (1-butenyl) phosphonate, ethylene (2-butenyl) phosphonate, ethylene (3 -Butenyl) phosphonate, ethylene (1-pentenyl) phosphonate, ethylene (2-pentenyl) phosphonate, ethylene (3-pentenyl) phosphonate, ethylene (4-pentenyl) phosphonate, ethylene ethynyl phosphonate, ethylene (1-propynyl) phosphonate, ethylene (2-propynyl) phosphonate, ethylene (1-butynyl) phosphonate, ethylene (2-butynyl) phosphonate, ethylene (3-butynyl) phospho Sulfonate, ethylene (1-pentynyl) phosphonate, ethylene (2-pentynyl) phosphonate, ethylene (3-pentynyl) phosphonate, ethylene (4-pentynyl) phosphonate, ethylene phenyl phosphonate, ethylene benzyl phosphonate, propylene methyl phosphonate, propylene ethyl phosphonate, Propylene propyl phosphonate, propylene butyl phosphonate, propylene pentyl phosphonate, propylene hexyl phosphonate, propylene heptyl phosphonate, propylene octyl phosphonate, propylene ethenyl phosphonate, propylene (1-propenyl) phosphonate, propylene (2-propenyl) phosphonate, propylene (1-butenyl) ) Phosphonate, propylene (2-butenyl) phosphate Phonate, propylene (3-butenyl) phosphonate, propylene (1-pentenyl) phosphonate, propylene (2-pentenyl) phosphonate, propylene (3-pentenyl) phosphonate, propylene (4-pentenyl) phosphonate, propylene ethynylphosphonate, propylene (1- Propynyl) phosphonate, propylene (2-propynyl) phosphonate, propylene (1-butynyl) phosphonate, propylene (2-butynyl) phosphonate, propylene (3-butynyl) phosphonate, propylene (1-pentynyl) phosphonate, propylene (2-pentynyl) Phosphonate, propylene (3-pentynyl) phosphonate, propylene (4-pentynyl) phosphonate, propylene phenylphosphonate, propylene Benzyl phosphonate, methylene methyl phosphate, methylene ethyl phosphate, methylene propyl phosphate, methylene butyl phosphate, methylene pentyl phosphate, methylene hexyl phosphate, methylene heptyl phosphate, methylene octyl phosphate, methylene ethenyl phosphate, Methylene (1-propenyl) phosphate, methylene (2-propenyl) phosphate, methylene (1-butenyl) phosphate, methylene (2-butenyl) phosphate, methylene (3-butenyl) phosphate, methylene (1-pentenyl) ) Phosphate, methylene (2-pentenyl) phosphate, methylene (3-pentenyl) phosphate, methylene (4-pentenyl) phosphate , Methylene ethynyl phosphate, methylene (1-propynyl) phosphate, methylene (2-propynyl) phosphate, methylene (1-butynyl) phosphate, methylene (2-butynyl) phosphate, methylene (3-butynyl) phosphate Fate, methylene (1-pentynyl) phosphate, methylene (2-pentynyl) phosphate, methylene (3-pentynyl) phosphate, methylene (4-pentynyl) phosphate, methylene phenyl phosphate, methylene benzyl phosphate, ethylene methyl Phosphate, ethylene ethyl phosphate, ethylene propyl phosphate, ethylene butyl phosphate, ethylene pentyl phosphate, ethylene hexyl phosphate, ethyl Nheptyl phosphate, ethylene octyl phosphate, ethylene ethenyl phosphate, ethylene (1-propenyl) phosphate, ethylene (2-propenyl) phosphate, ethylene (1-butenyl) phosphate, ethylene (2-butenyl) phosphate Fate, ethylene (3-butenyl) phosphate, ethylene (1-pentenyl) phosphate, ethylene (2-pentenyl) phosphate, ethylene (3-pentenyl) phosphate, ethylene (4-pentenyl) phosphate, ethylene ethynyl phosphate Fate, ethylene (1-propynyl) phosphate, ethylene (2-propynyl) phosphate, ethylene (1-butynyl) phosphate, ethylene (2-butynyl) phosphate, ethyl (3-butynyl) phosphate, ethylene (1-pentynyl) phosphate, ethylene (2-pentynyl) phosphate, ethylene (3-pentynyl) phosphate, ethylene (4-pentynyl) phosphate, ethylene phenyl phosphate, ethylene Benzyl phosphate, propylene methyl phosphate, propylene ethyl phosphate, propylene propyl phosphate, propylene butyl phosphate, propylene pentyl phosphate, propylene hexyl phosphate, propylene heptyl phosphate, propylene octyl phosphate, propylene ethenyl phosphate, Propylene (1-propenyl) phosphate, propylene (2-propenyl) phosphate, propylene (1 -Butenyl) phosphate, propylene (2-butenyl) phosphate, propylene (3-butenyl) phosphate, propylene (1-pentenyl) phosphate, propylene (2-pentenyl) phosphate, propylene (3-pentenyl) phosphate , Propylene (4-pentenyl) phosphate, propylene ethynyl phosphate, propylene (1-propynyl) phosphate, propylene (2-propynyl) phosphate, propylene (1-butynyl) phosphate, propylene (2-butynyl) phosphate , Propylene (3-butynyl) phosphate, propylene (1-pentynyl) phosphate, propylene (2-pentynyl) phosphate, propylene (3-pentynyl) phosphate Propylene (4-pentynyl) phosphate, propylene phenyl phosphate, propylene benzyl phosphate.
〔リチウム塩化合物(B)〕
本実施形態の非水電解液は、シュウ酸構造を有さないリチウム塩化合物(B)を含有する。「シュウ酸構造」とは、下記一般式(2)で表される化学構造を指し、本実施形態においては、単に「C2O4」とも表記する。
The non-aqueous electrolyte of this embodiment contains a lithium salt compound (B) that does not have an oxalic acid structure. The “oxalic acid structure” refers to a chemical structure represented by the following general formula (2). In the present embodiment, it is also simply expressed as “C 2 O 4 ”.
シュウ酸構造を有さないリチウム塩化合物(B)としては、分子内にシュウ酸構造を有さないリチウム塩化合物であれば、特に限定されないが、例えば、LiPF6、LiBF4、LiClO4、LiAsF6、LiSbF6、LiFSO3、LiCF3SO3、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2CF2CF3)2、LiN(SO2CF3)(SO2CF2CF3)、LiPO2F2、Li2PO3F、LiPF3(C3F7)3、LiB(CF3)4、LiB(CN)4を挙げることができる。この中でも、リチウム塩化合物(B)としては、入出力特性及びサイクル特性の両面を考慮し、LiPF6、LiBF4、LiN(SO2F)2、LiN(SO2CF3)2、LiN(SO2CF2CF3)2、LiPO2F2、Li2PO3Fからなる群より選ばれる一種を単独で、又は二種以上を組み合わせて用いることが好ましく、LiPF6とLiBF4及び/又はLiPO2F2とを組み合わせて用いることがより好ましい。 The lithium salt compound (B) having no oxalic acid structure is not particularly limited as long as it is a lithium salt compound having no oxalic acid structure in the molecule. For example, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiSbF 6 , LiFSO 3 , LiCF 3 SO 3 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 CF 3 ) 2 , LiN (SO 2 CF 3 ) (SO 2 CF 2 CF 3), LiPO 2 F 2, Li 2 PO 3 F, LiPF 3 (C 3 F 7) 3, LiB (CF 3) 4, can be cited LiB (CN) 4. Among these, as the lithium salt compound (B), in consideration of both input / output characteristics and cycle characteristics, LiPF 6 , LiBF 4 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 CF 2 CF 3 ) 2 , LiPO 2 F 2 , Li 2 PO 3 F are preferably used alone or in combination of two or more, and LiPF 6 and LiBF 4 and / or LiPO are used. it is more preferable to use in combination with 2 F 2.
リチウム塩化合物(B)の含有量は、入出力特性及びサイクル特性の両面を考慮して、非水電解液の総量に対して、好ましくは3質量%以上30質量%以下であり、より好ましくは5質量%以上25質量%以下であり、さらに好ましくは8質量%以上20質量%以下である。 The content of the lithium salt compound (B) is preferably 3% by mass or more and 30% by mass or less, more preferably, with respect to the total amount of the non-aqueous electrolyte in consideration of both input / output characteristics and cycle characteristics. It is 5 mass% or more and 25 mass% or less, More preferably, it is 8 mass% or more and 20 mass% or less.
〔リチウム塩化合物(C)〕
本実施形態の非水電解液は、シュウ酸構造を有するリチウム塩化合物(C)を含有する。シュウ酸構造を有するリチウム塩化合物(C)としては、分子内にシュウ酸構造を有するリチウム塩化合物であれば、特に限定されないが、例えば、Li2(C2O4)、LiB(C2O4)2、LiBF2(C2O4)、LiAl(C2O4)2、LiAlF2(C2O4)、LiP(C2O4)3、LiPF2(C2O4)2、LiPF4(C2O4)を挙げることができる。この中でも、リチウム塩化合物(C)としては、非水溶媒への溶解性及びガス発生抑制の両面を考慮して、LiB(C2O4)2、LiBF2(C2O4)、LiP(C2O4)3、LiPF2(C2O4)2、及びLiPF4(C2O4)からなる群より選ばれる一種以上が好ましく、LiB(C2O4)2、LiBF2(C2O4)がより好ましい。
[Lithium salt compound (C)]
The nonaqueous electrolytic solution of the present embodiment contains a lithium salt compound (C) having an oxalic acid structure. Examples of the lithium salt compound having the oxalic acid structure (C), if a lithium salt compound having the oxalic acid structure in the molecule is not particularly limited, for example, Li 2 (C 2 O 4 ), LiB (C 2 O 4) 2, LiBF 2 (C 2 O 4), LiAl (C 2 O 4) 2, LiAlF 2 (C 2 O 4), LiP (C 2 O 4) 3, LiPF 2 (C 2 O 4) 2, LiPF 4 (C 2 O 4 ) can be mentioned. Among these, as the lithium salt compound (C), LiB (C 2 O 4 ) 2 , LiBF 2 (C 2 O 4 ), LiP () are considered in consideration of both solubility in a non-aqueous solvent and gas generation suppression. One or more selected from the group consisting of C 2 O 4 ) 3 , LiPF 2 (C 2 O 4 ) 2 , and LiPF 4 (C 2 O 4 ) are preferable, and LiB (C 2 O 4 ) 2 , LiBF 2 (C 2 O 4 ) is more preferred.
リチウム塩化合物(C)の含有量は、ガス発生抑制の観点から、非水電解液の総量に対して、好ましくは0.01質量%以上10質量%以下であり、より好ましくは0.1質量%以上5質量%以下であり、さらに好ましくは0.3質量%以上3質量%以下である。 The content of the lithium salt compound (C) is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass with respect to the total amount of the non-aqueous electrolyte, from the viewpoint of suppressing gas generation. % To 5% by mass, and more preferably 0.3% to 3% by mass.
本実施形態の非水電解液においては、環状リン酸エステル(A)とリチウム塩化合物(C)とを組み合わせて用いる。本実施形態の非水電解液のガス発生抑制効果(電解液の分解抑制効果)をより高める観点からは、環状リン酸エステル(A)とリチウム塩化合物(C)を、それぞれ非水電解液に対して0.01質量%以上10質量%以下の含有量で、非水電解液中に共存させることが好ましい。上記濃度範囲でガス発生抑制効果が顕著に発揮されることから、リチウム塩化合物(C)の役割は、イオン伝導を担保することよりも、むしろ、正極及び負極の改質にあると考えられる。ガス発生が顕著に抑制される理由は、必ずしも明らかではない。すなわち、本実施形態の非水電解液が発揮する効果は、本段落で説明する作用ないし原理によるものに限定されないが、リチウム塩化合物(C)に含まれるシュウ酸部位と、環状リン酸エステル(A)の環状構造部位が、正極及び負極に協同的に作用することで、ガス発生を効果的に抑制しているものと考えられる。 In the nonaqueous electrolytic solution of the present embodiment, the cyclic phosphate ester (A) and the lithium salt compound (C) are used in combination. From the viewpoint of further enhancing the gas generation suppressing effect (electrolytic solution decomposition suppressing effect) of the nonaqueous electrolytic solution of the present embodiment, the cyclic phosphate ester (A) and the lithium salt compound (C) are each converted to a nonaqueous electrolytic solution. On the other hand, it is preferable to make it coexist in a non-aqueous electrolyte solution with a content of 0.01 mass% or more and 10 mass% or less. Since the gas generation suppression effect is remarkably exhibited in the above concentration range, it is considered that the role of the lithium salt compound (C) is in reforming the positive electrode and the negative electrode rather than ensuring ionic conduction. The reason why the gas generation is remarkably suppressed is not necessarily clear. That is, the effect exhibited by the nonaqueous electrolytic solution of the present embodiment is not limited to the action or principle described in this paragraph, but the oxalic acid moiety contained in the lithium salt compound (C) and the cyclic phosphate ( It is considered that the cyclic structure part A) effectively suppresses gas generation by acting cooperatively on the positive electrode and the negative electrode.
〔非水溶媒〕
本実施形態の非水電解液は、非水溶媒を含有する。上記非水溶媒としては、特に限定されず様々なものを用いることができるが、非プロトン性極性溶媒が好ましい。非プロトン性極性溶媒としては、特に限定されないが、例えば、エチレンカーボネート、プロピレンカーボネート、1,2−ブチレンカーボネート、2,3−ブチレンカーボネート、ビニレンカーボネート、ビニルエチレンカーボネート、トリフルオロメチルエチレンカーボネート、フルオロエチレンカーボネート及び4,5−ジフルオロエチレンカーボネートなどの環状カーボネート類;γーブチロラクトン及びγーバレロラクトンなどのラクトン類;スルホランなどのスルホン類;エチレンサルファイト、1,3−プロパンスルトンなどの亜硫酸エステル類;テトラヒドロフラン及びジオキサンなどの環状エーテル類;エチルメチルカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルプロピルカーボネート、メチルイソプロビルカーボネート、ジプロピルカーボネート、メチルブチルカーボネート、ジブチルカーボネート、エチルプロピルカーボネート及びメチルトリフルオロエチルカーボネートなどの鎖状カーボネート類;アセトニトリル及びプロピオニトリルなどのニトリル類;ジメチルエーテル及びジメトキシエタンなどの鎖状エーテル類;酢酸メチル及びプロピオン酸メチルなどの鎖状カルボン酸エステル類が挙げられる。これらは一種を単独で、又は二種以上を組み合わせて用いることができる。
[Nonaqueous solvent]
The nonaqueous electrolytic solution of the present embodiment contains a nonaqueous solvent. The non-aqueous solvent is not particularly limited and various solvents can be used, but an aprotic polar solvent is preferable. The aprotic polar solvent is not particularly limited. For example, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, vinylene carbonate, vinyl ethylene carbonate, trifluoromethyl ethylene carbonate, fluoroethylene. Cyclic carbonates such as carbonate and 4,5-difluoroethylene carbonate; lactones such as γ-butyrolactone and γ-valerolactone; sulfones such as sulfolane; sulfites such as ethylene sulfite and 1,3-propane sultone; tetrahydrofuran and Cyclic ethers such as dioxane; ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl iso Chain carbonates such as probil carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate and methyl trifluoroethyl carbonate; nitriles such as acetonitrile and propionitrile; chain ethers such as dimethyl ether and dimethoxyethane And chain carboxylic acid esters such as methyl acetate and methyl propionate. These can be used individually by 1 type or in combination of 2 or more types.
非水溶媒としては、環状カーボネートと鎖状カーボネートを特定の比率で混合したカーボネート溶媒を用いることが好ましい。環状カーボネートと鎖状カーボネートを混合する場合、環状カーボネートと鎖状カーボネートの混合比は、イオン伝導性の観点から、体積比で、好ましくは1:10〜5:1であり、より好ましくは1:5〜3:1であり、さらに好ましくは1:3〜2:1である。環状カーボネートとしては、特に限定されず様々なものを用いることができるが、例えば、エチレンカーボネート、プロピレンカーボネート、フルオロエチレンカーボネートが好ましく、エチレンカーボネート、プロピレンカーボネートがより好ましい。鎖状カーボネートとしては、特に限定されず様々なものを用いることができるが、例えば、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネートが好ましい。 As the non-aqueous solvent, it is preferable to use a carbonate solvent obtained by mixing a cyclic carbonate and a chain carbonate at a specific ratio. When mixing the cyclic carbonate and the chain carbonate, the mixing ratio of the cyclic carbonate and the chain carbonate is preferably 1:10 to 5: 1 by volume from the viewpoint of ion conductivity, and more preferably 1: It is 5-3: 1, More preferably, it is 1: 3-2: 1. Although it does not specifically limit as a cyclic carbonate and various things can be used, For example, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate are preferable, and ethylene carbonate and propylene carbonate are more preferable. The chain carbonate is not particularly limited, and various types can be used. For example, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate are preferable.
本実施形態の非水電解液は、非水蓄電デバイス用電解液として好適に用いられる。ここで、非水蓄電デバイスとは、蓄電デバイス中の電解液として水溶液を用いない蓄電デバイスの総称であり、特に限定されないが、例えば、リチウム二次電池、リチウムイオン二次電池、ナトリウム二次電池、ナトリウムイオン二次電池、マグネシウム二次電池、マグネシウムイオン二次電池、カルシウム二次電池、カルシウムイオン二次電池、アルミニウム二次電池、アルミニウムイオン二次電池、リチウムイオンキャパシタ、電気二重層キャパシタなどが挙げられる。上記の中でも、実用性の観点から、リチウム二次電池、リチウムイオン二次電池、リチウムイオンキャパシタが好ましく、より好ましくはリチウムイオン二次電池である。 The non-aqueous electrolyte of this embodiment is suitably used as an electrolyte for non-aqueous electricity storage devices. Here, the non-aqueous electricity storage device is a general term for an electricity storage device that does not use an aqueous solution as an electrolyte solution in the electricity storage device, and is not particularly limited. For example, a lithium secondary battery, a lithium ion secondary battery, a sodium secondary battery Sodium ion secondary battery, magnesium secondary battery, magnesium ion secondary battery, calcium secondary battery, calcium ion secondary battery, aluminum secondary battery, aluminum ion secondary battery, lithium ion capacitor, electric double layer capacitor, etc. Can be mentioned. Among these, from the viewpoint of practicality, a lithium secondary battery, a lithium ion secondary battery, and a lithium ion capacitor are preferable, and a lithium ion secondary battery is more preferable.
〔リチウムイオン二次電池〕
本実施形態のリチウムイオン二次電池は、正極と、負極と、本実施形態の非水電解液とを備え、満充電時の上記正極の電位がリチウム基準4.4V以上5.5V以下である。ここで、「満充電時の正極の電位」とは、充電電圧に満充電時の負極の電位を加えた値を指す。例えば、満充電時の電位がリチウム基準で約0.05Vになる黒鉛を負極活物質として単独で用いる場合、正極と黒鉛負極からなる電池を充電電圧4.35Vで満充電すると、満充電時の正極の電位はリチウム基準で約4.4Vとなる。満充電時の正極の電位は、三極式セルを用いて容易に測定することができる。具体的には、満充電状態の正極を作用極、リチウム金属を参照極、満充電状態の負極を対極とする構成の三極式セルを作製した場合、作用極と参照極の電位差が「満充電時の正極の電位」となる。
[Lithium ion secondary battery]
The lithium ion secondary battery of the present embodiment includes a positive electrode, a negative electrode, and the non-aqueous electrolyte of the present embodiment, and the potential of the positive electrode when fully charged is not less than 4.4 V and not more than 5.5 V based on lithium. . Here, the “positive electrode potential at full charge” refers to a value obtained by adding the negative electrode potential at full charge to the charge voltage. For example, when graphite having a fully charged potential of about 0.05 V with respect to lithium is used alone as the negative electrode active material, a battery consisting of a positive electrode and a graphite negative electrode is fully charged at a charging voltage of 4.35 V. The potential of the positive electrode is about 4.4 V with respect to lithium. The potential of the positive electrode at full charge can be easily measured using a tripolar cell. Specifically, when a three-electrode cell having a fully charged positive electrode as a working electrode, lithium metal as a reference electrode, and a fully charged negative electrode as a counter electrode is produced, the potential difference between the working electrode and the reference electrode is “full”. The potential of the positive electrode during charging ”.
〔正極〕
本実施形態において、満充電時の正極の電位としてリチウム基準4.4V以上の十分高い水準を確保する観点から、正極は、リチウム基準4.4V以上の電位でリチウムイオンを吸蔵、放出する正極活物質を単独で、又は二種以上を組み合わせて含有することが好ましい。
[Positive electrode]
In the present embodiment, from the viewpoint of ensuring a sufficiently high level of the lithium standard of 4.4 V or higher as the potential of the positive electrode at the time of full charge, the positive electrode is a positive electrode active that absorbs and releases lithium ions at a potential of the lithium standard of 4.4 V or higher. It is preferable to contain a substance alone or in combination of two or more.
(正極活物質)
リチウム基準4.4V以上の電位でリチウムイオンを吸蔵、放出する正極活物質としては、特に限定されないが、正極活物質の構造安定性の観点から、好ましくは、一般式LiNixCoyMa1−x−yO2〔Maは、Mn及びAlからなる群より選ばれる一種以上を表し、0≦x≦1であり、0≦y≦1であり、x+y≦1である。〕で示される層状酸化物正極活物質;一般式LiMn2−xMbxO4〔Mbは遷移金属からなる群より選ばれる一種以上を表し、0.2≦x≦0.7である。〕で示されるスピネル型酸化物正極活物質;Li2McO3とLiMdO2〔Mc及びMdは、各々独立して、遷移金属からなる群より選ばれる一種以上を表す。〕との複合酸化物であって、一般式zLi2McO3−(1−z)LiMdO2〔0.05≦z≦0.95である。〕で示されるLi過剰層状酸化物正極活物質;LiMe1−xFexPO4〔MeはMn及びCoからなる群より選ばれる一種以上を表し、0≦x≦1である。〕で示されるオリビン型正極活物質、及びLi2MfPO4F〔Mfは遷移金属からなる群より選ばれる一種以上を示す。〕からなる群より選ばれる一種以上の正極活物質などが挙げられる。
(Positive electrode active material)
The positive electrode active material that occludes and releases lithium ions at a potential of 4.4 V or higher with respect to lithium is not particularly limited. However, from the viewpoint of the structural stability of the positive electrode active material, the general formula LiNi x Co y Ma 1- x-y O 2 [Ma represents one or more selected from the group consisting of Mn and Al, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and x + y ≦ 1. A layered oxide positive electrode active material represented by the general formula: LiMn 2−x Mb x O 4 [Mb represents one or more selected from the group consisting of transition metals, and 0.2 ≦ x ≦ 0.7. A spinel oxide positive electrode active material represented by: Li 2 McO 3 and LiMdO 2 [Mc and Md each independently represents one or more selected from the group consisting of transition metals. And a general formula zLi 2 McO 3- (1-z) LiMdO 2 [0.05 ≦ z ≦ 0.95. Li-excess layered oxide positive electrode active material represented by: LiMe 1-x Fe x PO 4 [Me represents one or more selected from the group consisting of Mn and Co, and 0 ≦ x ≦ 1. And an olivine-type positive electrode active material represented by the formula: Li 2 MfPO 4 F [Mf represents one or more selected from the group consisting of transition metals. And one or more positive electrode active materials selected from the group consisting of:
一般式LiNixCoyMa1−x−yO2〔Maは、Mn及びAlからなる群より選ばれる一種以上を表し、0≦x≦1であり、0≦y≦1であり、x+y≦1である。〕で示される層状酸化物正極活物質としては、構造安定性の観点から、LiNixCoyMn1−x−yO2〔0≦x≦1であり、0≦y≦1であり、x+y≦1である。〕又はLiNixCoyAl1−x−yO2〔0.7≦x≦1であり、0≦y≦0.3であり、x+y≦1である。〕で示される組成を有することが好ましい。より好ましい組成としては、LiCoO2、LiNixCoyMn1−x−yO2〔0.4≦x≦1であり、0≦y≦0.4であり、x+y≦1である。〕、LiNi0.85Co0.1Al0.05O2を挙げることができる。 General formula LiNi x Co y Ma 1-xy O 2 [Ma represents one or more selected from the group consisting of Mn and Al, 0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and x + y ≦ 1. From the viewpoint of structural stability, the layered oxide positive electrode active material represented by the formula: LiNi x Co y Mn 1-xy O 2 [0 ≦ x ≦ 1, 0 ≦ y ≦ 1, and x + y ≦ 1. ] Or LiNi x Co y Al 1-xy O 2 [0.7 ≦ x ≦ 1, 0 ≦ y ≦ 0.3, and x + y ≦ 1. It is preferable to have a composition represented by More preferable compositions include LiCoO 2 , LiNi x Co y Mn 1-xy O 2 [0.4 ≦ x ≦ 1, 0 ≦ y ≦ 0.4, and x + y ≦ 1. And LiNi 0.85 Co 0.1 Al 0.05 O 2 .
一般式LiMn2−xMbxO4〔Mbは遷移金属からなる群より選ばれる一種以上を表し、0.2≦x≦0.7である。〕で示されるスピネル型酸化物正極活物質としては、構造安定性の観点から、LiMn2−xNixO4〔0.2≦x≦0.7である。〕で示される組成を有することが好ましい。より好ましい組成としては、LiMn1.5Ni0.5O4を挙げることができる。スピネル型酸化物には、構造安定性、電子伝導性などの観点から、Mn原子のモル数に対して30モル%以下の範囲で、上記構造以外にさらに遷移金属又は遷移金属酸化物を含有させることができる。 Formula LiMn 2-x Mb x O 4 [Mb represents at least one kind selected from the group consisting of transition metal, 0.2 ≦ x ≦ 0.7. The spinel oxide positive electrode active substance represented by], in view of structural stability, it is LiMn 2-x Ni x O 4 [0.2 ≦ x ≦ 0.7. It is preferable to have a composition represented by As a more preferred composition, LiMn 1.5 Ni 0.5 O 4 can be mentioned. From the viewpoint of structural stability, electronic conductivity, and the like, the spinel oxide further contains a transition metal or a transition metal oxide in addition to the above structure in a range of 30 mol% or less with respect to the number of moles of Mn atoms. be able to.
リチウムイオン二次電池を構成するための正極は、上記の正極活物質に、アセチレンブラックなどの導電助剤や、ポリフッ化ビニリデンなどの結着剤を適量加えて、正極合剤を調製し、これをアルミニウム箔などの集電材料に塗布乾燥後に加圧することで、集電材料上に正極合剤層を固着させて作製することができる。ただし、正極の作製方法は、上記例示のもののみに限定されない。 A positive electrode for constituting a lithium ion secondary battery was prepared by adding an appropriate amount of a conductive additive such as acetylene black and a binder such as polyvinylidene fluoride to the above positive electrode active material, and preparing a positive electrode mixture. Is applied to a current collecting material such as an aluminum foil and then pressurized, and then the positive electrode mixture layer can be fixed on the current collecting material. However, the method for manufacturing the positive electrode is not limited to the above-described examples.
〔負極〕
本実施形態のリチウムイオン二次電池に用いる負極は、負極活物質を含む。
[Negative electrode]
The negative electrode used for the lithium ion secondary battery of this embodiment contains a negative electrode active material.
(負極活物質)
本実施形態において、リチウムイオン二次電池を構成するための負極に用いることができる負極活物質としては、リチウムやリチウムイオンの吸蔵、放出が可能な化合物を使用することができる。上記負極活物質としては、特に限定されないが、例えば、Al、Si、Snなどの合金化合物;CuO、CoOなどの金属酸化物;チタン酸リチウムなどのリチウム含有化合物;及び炭素材料などを用いることができる。
(Negative electrode active material)
In this embodiment, as a negative electrode active material that can be used for a negative electrode for constituting a lithium ion secondary battery, lithium or a compound capable of occluding and releasing lithium ions can be used. The negative electrode active material is not particularly limited. For example, an alloy compound such as Al, Si, or Sn; a metal oxide such as CuO or CoO; a lithium-containing compound such as lithium titanate; and a carbon material may be used. it can.
本実施形態のリチウムイオン二次電池における負極活物質としては、電池のエネルギー密度向上の観点から、低電位でのリチウムイオンの吸蔵、放出が可能である炭素材料が好ましい。このような炭素材料としては、特に限定されないが、例えば、ハードカーボン、ソフトカーボン、人造黒鉛、天然黒鉛、熱分解炭素、コークス、ガラス状炭素、有機高分子化合物の焼成体、有機天然物の焼成体、炭素繊維、メソカーボンマイクロビーズ、カーボンブラックが挙げられる。上記コークスとしては、特に限定されないが、例えば、ピッチコークス、ニードルコークス及び石油コークスが挙げられる。また、有機高分子化合物の焼成体とは、フェノール樹脂などの高分子材料を適当な温度で焼成して炭素化したものを指し、有機天然物の焼成体とは、コーヒー殻などの天然由来材料を適当な温度で焼成して炭素化したものを指す。 As the negative electrode active material in the lithium ion secondary battery of the present embodiment, a carbon material capable of occluding and releasing lithium ions at a low potential is preferable from the viewpoint of improving the energy density of the battery. Such a carbon material is not particularly limited. For example, hard carbon, soft carbon, artificial graphite, natural graphite, pyrolytic carbon, coke, glassy carbon, a fired body of an organic polymer compound, firing of an organic natural product Body, carbon fiber, mesocarbon microbeads, carbon black. Although it does not specifically limit as said coke, For example, pitch coke, needle coke, and petroleum coke are mentioned. In addition, a fired body of an organic polymer compound refers to a carbon material obtained by firing a polymer material such as a phenol resin at an appropriate temperature, and a fired body of an organic natural product refers to a naturally derived material such as coffee husk. Refers to carbonized by firing at an appropriate temperature.
負極活物質に炭素材料を用いる場合、該炭素材料の(002)面の層間距離d002は好ましくは0.37nm以下であり、より好ましくは0.35nm以下であり、さらに好ましくは0.34nm以下である。d002の下限値は特に限定されないが、理論的には約0.335nmである。 When a carbon material is used for the negative electrode active material, the interlayer distance d002 of the (002) plane of the carbon material is preferably 0.37 nm or less, more preferably 0.35 nm or less, and further preferably 0.34 nm or less. is there. The lower limit of d002 is not particularly limited, but is theoretically about 0.335 nm.
また、炭素材料のc軸方向の結晶子の大きさは、好ましくは3nm以上であり、より好ましくは8nm以上であり、さらに好ましくは25nm以上である。結晶子の大きさの上限は、特に限定されないが、通例200nm程度である。そして、炭素材料の平均粒径は、好ましくは3μm以上15μm以下であり、より好ましくは5μm以上13μm以下である。また、その純度は、99.9%以上であることが好ましい。 Further, the size of the crystallite in the c-axis direction of the carbon material is preferably 3 nm or more, more preferably 8 nm or more, and further preferably 25 nm or more. The upper limit of the crystallite size is not particularly limited, but is usually about 200 nm. And the average particle diameter of a carbon material becomes like this. Preferably they are 3 micrometers or more and 15 micrometers or less, More preferably, they are 5 micrometers or more and 13 micrometers or less. Moreover, it is preferable that the purity is 99.9% or more.
リチウムイオン二次電池を構成するための負極は、上記の負極活物質に、カルボキシメチルセルロースなどの増粘剤や、スチレンブタジエンゴムなどの結着剤を適量加えて、負極合剤を調製し、これを銅箔などの集電材料に塗布乾燥後に加圧することで、集電材料上に負極合剤層を固着させて作製することができる。ただし、負極の作製方法は、上記例示のもののみに限定されない。 A negative electrode for constituting a lithium ion secondary battery was prepared by adding an appropriate amount of a thickener such as carboxymethyl cellulose and a binder such as styrene butadiene rubber to the above negative electrode active material, and preparing a negative electrode mixture. Is applied to a current collecting material such as a copper foil and then pressed, and then the negative electrode mixture layer can be fixed on the current collecting material. However, the method for manufacturing the negative electrode is not limited to the above-described examples.
〔セパレータ〕
本実施形態のリチウムイオン二次電池は、正負極の短絡防止などの安全性付与の観点から、正極と負極の間にセパレータを備えることが好ましい。上記セパレータとしては、特に限定されず、従来公知のリチウムイオン二次電池で採用されている各種セパレータを用いることができる。例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂;ポリエチレンテレフタラートなどのポリエステル系樹脂;ポリアラミドなどのポリアミド樹脂に代表される樹脂類を成形した微多孔膜又は不織布などが好適に用いられる。安全性付与の観点から、セパレータの厚みは、好ましくは5μm以上であり、より好ましくは10μm以上である。一方、電池の入出力特性を維持する観点から、セパレータの厚みは、好ましくは30μm以下であり、より好ましくは20μm以下である。
[Separator]
The lithium ion secondary battery of this embodiment preferably includes a separator between the positive electrode and the negative electrode from the viewpoint of providing safety such as prevention of short circuit between the positive and negative electrodes. The separator is not particularly limited, and various separators employed in conventionally known lithium ion secondary batteries can be used. For example, a polyolefin resin such as polyethylene or polypropylene; a polyester resin such as polyethylene terephthalate; a microporous film or a nonwoven fabric formed by molding a resin represented by a polyamide resin such as polyaramid is preferably used. From the viewpoint of imparting safety, the thickness of the separator is preferably 5 μm or more, and more preferably 10 μm or more. On the other hand, from the viewpoint of maintaining the input / output characteristics of the battery, the thickness of the separator is preferably 30 μm or less, and more preferably 20 μm or less.
本実施形態のリチウムイオン二次電池は、例えば、上述の正極と負極とを、セパレータを介して重ね合わせて、必要に応じて巻回して、積層電極体又は巻回電極体とした後、これを外装体に装填し、正負極と外装体の正負極端子とをリード体などを介して接続し、さらに上記本実施形態の非水電解液を外装体内に注入した後に外装体を封止して作製することができる。上記電池の外装体としては、特に限定されないが、金属製の缶容器や、金属箔ラミネートフィルムからなるラミネート容器などを好適に用いることができる。なお、リチウムイオン二次電池の形状としては、特に限定されず、一例を挙げると、円筒形、角型、コイン型、扁平形、シート状などの形状が採用される。 The lithium ion secondary battery of the present embodiment includes, for example, the above-described positive electrode and negative electrode that are overlapped via a separator and wound as necessary to obtain a laminated electrode body or a wound electrode body. Is attached to the exterior body, the positive and negative electrodes and the positive and negative terminals of the exterior body are connected via a lead body, and the nonaqueous electrolyte of the present embodiment is injected into the exterior body, and then the exterior body is sealed. Can be produced. Although it does not specifically limit as an exterior body of the said battery, The laminated container etc. which consist of metal can containers, a metal foil laminated film, etc. can be used conveniently. The shape of the lithium ion secondary battery is not particularly limited. For example, a cylindrical shape, a square shape, a coin shape, a flat shape, a sheet shape, or the like is adopted.
本実施形態のリチウムイオン二次電池は、エネルギー密度が高く、実用上の耐久性にも優れることから、携帯電話などのモバイル電子機器用電源としてのみならず、様々な機器の電源として幅広く利用することができる。 The lithium ion secondary battery of this embodiment has high energy density and excellent practical durability, so it is widely used not only as a power source for mobile electronic devices such as mobile phones but also as a power source for various devices. be able to.
以下、実施例に基づいて本発明をさらに詳細に説明するが、本発明は、その要旨を超えない限り、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples, unless the summary is exceeded.
[実施例1]
1:正極の製造
正極活物質としてLiNi1/3Co1/3Mn1/3O2(日本化学工業社製)と、導電助剤としてアセチレンブラックの粉末(電気化学工業社製)と、バインダーとしてポリフッ化ビニリデン溶液(クレハ社製)とを、90:6:4の固形分質量比で混合し、分散溶媒としてN−メチル−2−ピロリドンを固形分40質量%となるように添加してさらに混合して、スラリー状の溶液を調製した。このスラリー状の溶液を厚さ20μmのアルミニウム箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延して正極とした。
[Example 1]
1: Production of positive electrode LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Nippon Kagaku Kogyo Co., Ltd.) as a positive electrode active material, acetylene black powder (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive additive, and binder As a dispersion solvent, a polyvinylidene fluoride solution (manufactured by Kureha Co., Ltd.) is mixed at a solid content mass ratio of 90: 6: 4, and N-methyl-2-pyrrolidone is added as a dispersion solvent to a solid content of 40% by mass. Further mixing was performed to prepare a slurry solution. This slurry-like solution was applied to one side of an aluminum foil having a thickness of 20 μm, and the solvent was removed by drying, followed by rolling with a roll press to obtain a positive electrode.
2:負極の製造
負極活物質としてグラファイト粉末(大阪ガスケミカル社製)及びグラファイト粉末(TIMCAL社製)と、バインダーとしてスチレンブタジエンゴム及びカルボキシメチルセルロース水溶液を、90:10:1.5:1.8の固形分質量比で混合し、分散溶媒として水を固形分45質量%となるように添加してさらに混合して、スラリー状の溶液を調製した。このスラリー状の溶液を厚さ18μmの銅箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延して負極とした。
2: Production of negative electrode Graphite powder (manufactured by Osaka Gas Chemical Co., Ltd.) and graphite powder (manufactured by TIMCAL) as a negative electrode active material, and styrene-butadiene rubber and carboxymethylcellulose aqueous solution as a binder, 90: 10: 1.5: 1.8 Were mixed at a solid content mass ratio of water, water was added as a dispersion solvent so as to have a solid content of 45 mass%, and further mixed to prepare a slurry solution. This slurry-like solution was applied to one side of a copper foil having a thickness of 18 μm, and after removing the solvent by drying, it was rolled with a roll press to obtain a negative electrode.
3:非水電解液の調製
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)とを体積比1:2で混合した混合溶媒に、エチレン(3−ブチニル)フォスフェートを0.3質量%と、LiPF6を12.1質量%と、LiB(C2O4)2を1質量%と、を添加、混合して非水電解液を調製した。
3: Preparation of non-aqueous electrolyte solution In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, ethylene (3-butynyl) phosphate was 0.3% by mass; A nonaqueous electrolytic solution was prepared by adding and mixing LiPF 6 (12.1% by mass) and LiB (C 2 O 4 ) 2 (1% by mass).
4:試験用電池の作製
上述のようにして作製した正極と負極とを、ポリプロピレン製の微多孔膜からなるセパレータ(膜厚25μm、空孔率50%、孔径0.1μm〜1μm)の両側に重ね合わせた積層体を、アルミニウム箔(厚さ40μm)の両面を樹脂層で被覆したラミネートフィルムからなる袋内に正負極の端子を突設させながら挿入した後、上述のようにして調製した非水電解液を袋内に注入し、真空封止を行って、シート状リチウムイオン二次電池を作製した。
4: Production of test battery The positive electrode and the negative electrode produced as described above were placed on both sides of a separator (thickness 25 μm, porosity 50%, pore diameter 0.1 μm to 1 μm) made of a polypropylene microporous film. The stacked laminate was inserted into a bag made of a laminate film in which both sides of an aluminum foil (thickness 40 μm) were covered with a resin layer while projecting positive and negative terminals, and then prepared as described above. A water electrolyte was poured into the bag and vacuum sealed to produce a sheet-like lithium ion secondary battery.
5:試験用電池の評価
5−1:初充放電
得られたシート状電池を、25℃の環境下、0.05Cの定電流で4.35Vの電圧に達するまで充電後(満充電時の正極電位=4.4V)、4.35Vの定電圧で2時間充電し、0.2Cの定電流で3.0Vまで放電した。これを3サイクル繰り返した。なお、1Cとは電池の基準容量を1時間で放電する電流値を表し、0.05Cとはその1/20の電流値を表す。
5: Evaluation of test battery 5-1: Initial charge / discharge After charging the obtained sheet-like battery at a constant current of 0.05 C until reaching a voltage of 4.35 V in an environment of 25 ° C. (Positive electrode potential = 4.4V) The battery was charged at a constant voltage of 4.35V for 2 hours and discharged to 3.0V at a constant current of 0.2C. This was repeated for 3 cycles. Note that 1C represents a current value for discharging the reference capacity of the battery in one hour, and 0.05C represents a current value of 1/20.
5−2:サイクル試験
初充放電後の電池を、50℃の環境下、1Cの定電流で4.35Vの電圧に達するまで充電後、4.35Vの定電圧で1時間充電し、1Cの定電流で3.0Vまで放電した。上記一連の充放電を1サイクルとして、これを100サイクル実施し、100サイクル後容量維持率を測定した。その結果、100サイクル後容量維持率は90%と高かった。なお、100サイクル後容量維持率は、以下の式で求めた。
100サイクル後容量維持率(%)=(100サイクル目の放電容量/1サイクル目の放電容量)×100
5-2: Cycle test The battery after initial charge / discharge is charged at a constant current of 1C until reaching a voltage of 4.35V under an environment of 50 ° C, and then charged at a constant voltage of 4.35V for 1 hour. The battery was discharged at a constant current to 3.0V. The above series of charging / discharging was made into 1 cycle, this was implemented 100 cycles, and the capacity maintenance rate was measured after 100 cycles. As a result, the capacity retention rate after 100 cycles was as high as 90%. The capacity retention rate after 100 cycles was determined by the following formula.
Capacity maintenance rate after 100 cycles (%) = (discharge capacity at the 100th cycle / discharge capacity at the first cycle) × 100
5−3:ガス発生試験
初充放電後の電池を、水浴中に浸して体積を測定した後、50℃の環境下、1Cの定電流で4.35Vの電圧に達するまで充電後、4.35Vの定電圧で一週間連続充電し、1Cの定電流で3.0Vまで放電した。
電池を室温まで冷却させた後、水浴中に浸して体積を測定し、連続充電前後の電池の体積変化から、連続充電後発生ガス量を求めた。その結果、連続充電後発生ガス量は0.17mLと少なかった。
5-3: Gas generation test The battery after initial charge / discharge was immersed in a water bath and the volume was measured. After charging, the battery was charged at a constant current of 1 C until reaching a voltage of 4.35 V in an environment of 50 ° C. The battery was continuously charged at a constant voltage of 35V for one week and discharged to 3.0V at a constant current of 1C.
After the battery was cooled to room temperature, it was immersed in a water bath to measure the volume, and the amount of gas generated after continuous charging was determined from the volume change of the battery before and after continuous charging. As a result, the amount of gas generated after continuous charging was as small as 0.17 mL.
[実施例2]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレン(2−プロピニル)フォスフェートを用いた以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は89%と高く、連続充電後発生ガス量は0.21mLと少なかった。
[Example 2]
A sheet battery was prepared in the same manner as in Example 1 except that ethylene (2-propynyl) phosphate was used instead of ethylene (3-butynyl) phosphate in the preparation of the nonaqueous electrolytic solution of Example 1. The cycle test and the gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 89%, and the amount of gas generated after continuous charging was as low as 0.21 mL.
[実施例3]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレン(3−ブテニル)フォスフェートを用いた以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は90%と高く、連続充電後発生ガス量は0.17mLと少なかった。
[Example 3]
A sheet-like battery was prepared in the same manner as in Example 1 except that ethylene (3-butenyl) phosphate was used instead of ethylene (3-butynyl) phosphate in the preparation of the nonaqueous electrolytic solution of Example 1. The cycle test and the gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 90%, and the amount of gas generated after continuous charging was as small as 0.17 mL.
[実施例4]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレンヘキシルホスホネートを用いた以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は88%と高く、連続充電後発生ガス量は0.27mLと少なかった。
[Example 4]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that ethylene hexyl phosphonate was used instead of ethylene (3-butynyl) phosphate. A gas generation test was conducted. As a result, the capacity retention rate after 100 cycles was as high as 88%, and the amount of gas generated after continuous charging was as small as 0.27 mL.
[実施例5]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレンオクチルフォスフェートを用いた以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は89%と高く、連続充電後発生ガス量は0.23mLと少なかった。
[Example 5]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that ethylene octyl phosphate was used instead of ethylene (3-butynyl) phosphate. And a gas generation test was conducted. As a result, the capacity retention rate after 100 cycles was as high as 89%, and the amount of gas generated after continuous charging was as small as 0.23 mL.
[実施例6]
実施例1の非水電解液の調製において、混合溶媒に、さらにLiBF4を0.5質量%添加した以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は91%と高く、連続充電後発生ガス量は0.17mLと少なかった。
[Example 6]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that 0.5% by mass of LiBF 4 was further added to the mixed solvent, and the above cycle test and gas generation test were performed. Went. As a result, the capacity retention rate after 100 cycles was as high as 91%, and the amount of gas generated after continuous charging was as small as 0.17 mL.
[実施例7]
実施例1の非水電解液の調製において、混合溶媒に、さらにLiPO2F2を0.5質量%添加した以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は92%と高く、連続充電後発生ガス量は0.15mLと少なかった。
[Example 7]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that 0.5% by mass of LiPO 2 F 2 was further added to the mixed solvent. A developmental test was performed. As a result, the capacity retention rate after 100 cycles was as high as 92%, and the amount of gas generated after continuous charging was as small as 0.15 mL.
[実施例8]
実施例1の非水電解液の調製において、LiB(C2O4)2の代わりに、LiPF2(C2O4)2を用いた以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は89%と高く、連続充電後発生ガス量は0.19mLと少なかった。
[Example 8]
A sheet-like battery was produced in the same manner as in Example 1 except that LiPF 2 (C 2 O 4 ) 2 was used instead of LiB (C 2 O 4 ) 2 in the preparation of the non-aqueous electrolyte of Example 1. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 89%, and the amount of gas generated after continuous charging was as small as 0.19 mL.
[実施例9]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートを0.3質量%添加する代わりに、1質量%添加した以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は88%と高く、連続充電後発生ガス量は0.15mLと少なかった。
[Example 9]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that 1% by mass was added instead of 0.3% by mass of ethylene (3-butynyl) phosphate. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 88%, and the amount of gas generated after continuous charging was as small as 0.15 mL.
[実施例10]
実施例1の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートを0.3質量%添加する代わりに、3質量%添加した以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は86%と高く、連続充電後発生ガス量は0.11mLと少なかった。
[Example 10]
In the preparation of the nonaqueous electrolytic solution of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that 3% by mass was added instead of 0.3% by mass of ethylene (3-butynyl) phosphate. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 86%, and the amount of gas generated after continuous charging was as small as 0.11 mL.
[比較例1]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は76%と低く、連続充電後発生ガス量は0.54mLと多かった。
[Comparative Example 1]
12.1% by mass of LiPF 6 was added to a mixed solvent obtained by mixing ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 1: 2 to obtain a nonaqueous electrolytic solution. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 76%, and the amount of gas generated after continuous charging was as large as 0.54 mL.
[比較例2]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は88%と低く、連続充電後発生ガス量は0.34mLと多かった。
[Comparative Example 2]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 2, LiPF 6 is 12.1% by mass, LiB (C 2 O 4 ) 2 is 1% by mass, Was added to obtain a non-aqueous electrolyte. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and a cycle test and a gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 88%, and the amount of gas generated after continuous charging was as large as 0.34 mL.
[比較例3]
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)とを体積比1:2で混合した混合溶媒に、エチレン(3−ブチニル)フォスフェートを0.3質量%と、LiPF6を12.1質量%と、を添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は82%と低く、連続充電後発生ガス量は0.28mLと多かった。
[Comparative Example 3]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, ethylene (3-butynyl) phosphate was 0.3% by mass, and LiPF 6 was 12.1% by mass. To make a non-aqueous electrolyte. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 82%, and the amount of gas generated after continuous charging was as large as 0.28 mL.
[比較例4]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%と、LiBF4を0.5質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は84%と低く、連続充電後発生ガス量は0.32mLと多かった。
[Comparative Example 4]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, LiPF 6 was 12.1% by mass, LiBF 4 was 0.5% by mass, and LiB (C 2 1 mass% of O 4 ) 2 was added to make a non-aqueous electrolyte. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 84%, and the amount of gas generated after continuous charging was as large as 0.32 mL.
[比較例5]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%と、LiPO2F2を0.5質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は88%と低く、連続充電後発生ガス量は0.28mLと多かった。
[Comparative Example 5]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, LiPF 6 was 12.1% by mass, LiPO 2 F 2 was 0.5% by mass, and LiB ( C 2 O 4 ) 2 was added in an amount of 1% by mass to obtain a non-aqueous electrolyte. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 88%, and the amount of gas generated after continuous charging was as large as 0.28 mL.
[比較例6]
エチレンカーボネート(EC)とジメチルカーボネート(DMC)と2,2,2−トリフルオロエチルエチレンフォスフェートを体積比42.5:42.5:15で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は79%と低く、連続充電後発生ガス量は0.31mLと多かった。
[Comparative Example 6]
12.1 mass of LiPF 6 in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC) and 2,2,2-trifluoroethyl ethylene phosphate were mixed at a volume ratio of 42.5: 42.5: 15 % To make a non-aqueous electrolyte. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 79%, and the amount of gas generated after continuous charging was as large as 0.31 mL.
[比較例7]
2−メトキシ−1,3,2−ジオキサフォスフォラン−2−オキサイドとジエチルカーボネート(DEC)を体積比1:1で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例1の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例1と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は58%と非常に低く、連続充電後発生ガス量は0.21mLと少なかった。
[Comparative Example 7]
To a mixed solvent in which 2-methoxy-1,3,2-dioxaphosphorane-2-oxide and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 1, 12.1% by mass of LiPF 6 was added and non-aqueous. An electrolyte was used. In the production of the test battery of Example 1, a sheet-like battery was produced in the same manner as in Example 1 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as very low as 58%, and the amount of gas generated after continuous charging was as low as 0.21 mL.
以上の実施例1〜10、及び比較例1〜7で得られた結果を、表1に示す。表1から、実施例1〜10のリチウムイオン二次電池はいずれも、環状リン酸エステル(A)を含まない非水電解液を用いた比較例2、4、及び5、シュウ酸構造を有するリチウム塩化合物(C)を含まない非水電解液を用いた比較例3と比して、サイクル特性が向上し、ガス発生量が低減していることが明らかとなった。以上より、本実施形態の非水電解液の上記効果は、非水電解液中に環状リン酸エステル(A)とシュウ酸構造を有するリチウム塩化合物(C)を共存させた場合に、特有の効果であることが示された。 Table 1 shows the results obtained in Examples 1 to 10 and Comparative Examples 1 to 7. From Table 1, all of the lithium ion secondary batteries of Examples 1 to 10 have Comparative Examples 2, 4, and 5 using a nonaqueous electrolytic solution that does not contain the cyclic phosphate ester (A), and an oxalic acid structure. It was revealed that the cycle characteristics were improved and the gas generation amount was reduced as compared with Comparative Example 3 using a non-aqueous electrolyte solution containing no lithium salt compound (C). From the above, the above-described effect of the nonaqueous electrolytic solution of the present embodiment is unique when the cyclic phosphate (A) and the lithium salt compound (C) having an oxalic acid structure coexist in the nonaqueous electrolytic solution. It was shown to be an effect.
また、実施例1〜10のリチウムイオン二次電池はいずれも、特許文献3に記載されている2,2,2−トリフルオロエチルエチレンフォスフェートを非水溶媒に対して15体積%含有させた比較例6、特許文献4に記載されている2−メトキシ−1,3,2−ジオキサフォスフォラン−2−オキサイドを非水溶媒に対して50体積%含有させた比較例7と比して、サイクル特性が大幅に向上し、ガス発生量が低減していることが明確となった。 Moreover, all the lithium ion secondary batteries of Examples 1 to 10 contained 15% by volume of 2,2,2-trifluoroethylethylene phosphate described in Patent Document 3 with respect to the nonaqueous solvent. Compared to Comparative Example 6 and Comparative Example 7 containing 50% by volume of 2-methoxy-1,3,2-dioxaphosphorane-2-oxide described in Patent Document 4 with respect to the non-aqueous solvent It was clarified that the cycle characteristics were greatly improved and the gas generation amount was reduced.
[実施例11]
1:正極活物質の製造
遷移金属元素のモル比として1:3の割合の硫酸ニッケルと硫酸マンガンとを、水に溶解し、金属イオン濃度の総和が2mol/Lになるようにニッケル−マンガン混合水溶液を調製した。次いで、このニッケル−マンガン混合水溶液を、70℃に加温した濃度2mol/Lの炭酸ナトリウム水溶液1650mL中に、12.5mL/minの添加速度で120分間滴下した。なお、滴下時には、撹拌の下、200mL/minの流量の空気を水溶液中にバブリングしながら吹き込んだ。これにより析出物質が発生し、得られた析出物質を蒸留水で十分洗浄し、乾燥して、ニッケルマンガン化合物を得た。得られたニッケルマンガン化合物と粒径2μmの炭酸リチウムとを、リチウム:ニッケル:マンガンのモル比が1:0.5:1.5になるように秤量し、1時間乾式混合した後、得られた混合物を酸素雰囲気下において1000℃で5時間焼成し、LiNi0.5Mn1.5O4で表される正極活物質を得た。
[Example 11]
1: Manufacture of positive electrode active material Nickel sulfate and manganese sulfate at a molar ratio of transition metal element of 1: 3 are dissolved in water and mixed with nickel-manganese so that the total concentration of metal ions is 2 mol / L. An aqueous solution was prepared. Subsequently, this nickel-manganese mixed aqueous solution was dropped into 1650 mL of a 2 mol / L sodium carbonate aqueous solution heated to 70 ° C. at an addition rate of 12.5 mL / min for 120 minutes. In addition, at the time of dripping, air with a flow rate of 200 mL / min was bubbled into the aqueous solution while stirring. As a result, a precipitated substance was generated, and the obtained precipitated substance was sufficiently washed with distilled water and dried to obtain a nickel manganese compound. The obtained nickel-manganese compound and lithium carbonate having a particle size of 2 μm were weighed so that the molar ratio of lithium: nickel: manganese was 1: 0.5: 1.5, and obtained after dry-mixing for 1 hour. The obtained mixture was baked at 1000 ° C. for 5 hours in an oxygen atmosphere to obtain a positive electrode active material represented by LiNi 0.5 Mn 1.5 O 4 .
2:正極の製造
上述のようにして得られた正極活物質と、導電助剤としてアセチレンブラックの粉末(電気化学工業社製)と、バインダーとしてポリフッ化ビニリデン溶液(クレハ社製)とを、88:6:6の固形分質量比で混合し、分散溶媒としてN−メチル−2−ピロリドンを固形分40質量%となるように添加してさらに混合して、スラリー状の溶液を調製した。このスラリー状の溶液を厚さ20μmのアルミニウム箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延して正極とした。
2: Production of positive electrode A positive electrode active material obtained as described above, an acetylene black powder (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a conductive auxiliary agent, and a polyvinylidene fluoride solution (manufactured by Kureha Co., Ltd.) as a binder, The mixture was mixed at a solid content mass ratio of 6: 6, N-methyl-2-pyrrolidone as a dispersion solvent was added so as to have a solid content of 40% by mass, and further mixed to prepare a slurry solution. This slurry-like solution was applied to one side of an aluminum foil having a thickness of 20 μm, and the solvent was removed by drying, followed by rolling with a roll press to obtain a positive electrode.
3:負極の製造
負極活物質としてのグラファイト粉末(大阪ガスケミカル社製)及びグラファイト粉末(TIMCAL社製)と、バインダーとしてのスチレンブタジエンゴム及びカルボキシメチルセルロース水溶液とを、90:10:1.5:1.8の固形分質量比で混合し、分散溶媒として水を固形分45質量%となるように添加してさらに混合して、スラリー状の溶液を調製した。このスラリー状の溶液を厚さ18μmの銅箔の片面に塗布し、溶剤を乾燥除去した後、ロールプレスで圧延して負極とした。
3: Production of negative electrode Graphite powder (manufactured by Osaka Gas Chemical Company) and graphite powder (manufactured by TIMCAL) as a negative electrode active material, styrene butadiene rubber and carboxymethyl cellulose aqueous solution as a binder, 90: 10: 1.5: The mixture was mixed at a solid content mass ratio of 1.8, water was added as a dispersion solvent so as to have a solid content of 45 mass%, and further mixed to prepare a slurry solution. This slurry-like solution was applied to one side of a copper foil having a thickness of 18 μm, and after removing the solvent by drying, it was rolled with a roll press to obtain a negative electrode.
4:非水電解液の調製
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)とを体積比1:2で混合した混合溶媒に、エチレン(3−ブチニル)フォスフェートを0.3質量%と、LiPF6を12.1質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。
4: Preparation of non-aqueous electrolyte In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, ethylene (3-butynyl) phosphate was 0.3% by mass; LiPF 6 (12.1% by mass) and LiB (C 2 O 4 ) 2 (1% by mass) were added to obtain a non-aqueous electrolyte.
5:試験用電池の作製
上述のようにして作製した正極と負極とを、ポリプロピレン製の微多孔膜からなるセパレータ(膜厚25μm、空孔率50%、孔径0.1μm〜1μm)の両側に重ね合わせた積層体を、アルミニウム箔(厚さ40μm)の両面を樹脂層で被覆したラミネートフィルムからなる袋内に正負極の端子を突設させながら挿入した後、上述のようにして調製した非水電解液を袋内に注入し、真空封止を行って、シート状リチウムイオン二次電池を作製した。
5: Production of test battery The positive electrode and the negative electrode produced as described above were placed on both sides of a separator (thickness 25 μm, porosity 50%, pore diameter 0.1 μm to 1 μm) made of a polypropylene microporous film. The stacked laminate was inserted into a bag made of a laminate film in which both sides of an aluminum foil (thickness 40 μm) were covered with a resin layer while projecting positive and negative terminals, and then prepared as described above. A water electrolyte was poured into the bag and vacuum sealed to produce a sheet-like lithium ion secondary battery.
6:試験用電池の評価
6−1:初充放電
得られたシート状電池を、25℃の環境下、0.05Cの定電流で4.8Vの電圧に達するまで充電後(満充電時の正極電位=4.85V)、4.8Vの定電圧で2時間充電し、0.2Cの定電流で3.0Vまで放電した。これを3サイクル繰り返した。なお、1Cとは電池の基準容量を1時間で放電する電流値を表し、0.05Cとはその1/20の電流値を表す。
6: Evaluation of test battery 6-1: Initial charge / discharge After charging the obtained sheet-like battery at a constant current of 0.05 C until reaching a voltage of 4.8 V in an environment of 25 ° C. (Positive electrode potential = 4.85V) The battery was charged at a constant voltage of 4.8V for 2 hours and discharged to 3.0V at a constant current of 0.2C. This was repeated for 3 cycles. Note that 1C represents a current value for discharging the reference capacity of the battery in one hour, and 0.05C represents a current value of 1/20.
6−2:サイクル試験
初充放電後の電池を、50℃の環境下、1Cの定電流で4.8Vの電圧に達するまで充電後、4.8Vの定電圧で1時間充電し、1Cの定電流で3.0Vまで放電した。上記一連の充放電を1サイクルとして、これを100サイクル実施し、100サイクル後容量維持率を測定した。その結果、100サイクル後容量維持率は74%と高かった。なお、100サイクル後容量維持率は、以下の式で求めた。
100サイクル後容量維持率(%)=(100サイクル目の放電容量/1サイクル目の放電容量)×100
6-2: Cycle test The battery after initial charge / discharge is charged at a constant current of 1C until reaching a voltage of 4.8V under an environment of 50 ° C, and then charged at a constant voltage of 4.8V for 1 hour. The battery was discharged at a constant current to 3.0V. The above series of charging / discharging was made into 1 cycle, this was implemented 100 cycles, and the capacity maintenance rate was measured after 100 cycles. As a result, the capacity retention rate after 100 cycles was as high as 74%. The capacity retention rate after 100 cycles was determined by the following formula.
Capacity maintenance rate after 100 cycles (%) = (discharge capacity at the 100th cycle / discharge capacity at the first cycle) × 100
6−3:ガス発生試験
初充放電後の電池を、水浴中に浸して体積を測定した後、50℃の環境下、1Cの定電流で4.8Vの電圧に達するまで充電後、4.8Vの定電圧で一週間連続充電し、1Cの定電流で3.0Vまで放電した。
電池を室温まで冷却させた後、水浴中に浸して体積を測定し、連続充電前後の電池の体積変化から、連続充電後発生ガス量を求めた。その結果、連続充電後発生ガス量は1.16mLと少なかった。
6-3: Gas generation test The battery after initial charge and discharge was immersed in a water bath and the volume was measured. After charging, the battery was charged at a constant current of 1 C until reaching a voltage of 4.8 V in an environment of 50 ° C. The battery was continuously charged at a constant voltage of 8V for one week and discharged to 3.0V at a constant current of 1C.
After the battery was cooled to room temperature, it was immersed in a water bath to measure the volume, and the amount of gas generated after continuous charging was determined from the volume change of the battery before and after continuous charging. As a result, the amount of gas generated after continuous charging was as small as 1.16 mL.
[実施例12]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレン(2−プロピニル)フォスフェートを用いた以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は70%と高く、連続充電後発生ガス量は1.23mLと少なかった。
[Example 12]
A sheet-like battery was prepared in the same manner as in Example 11 except that ethylene (2-propynyl) phosphate was used instead of ethylene (3-butynyl) phosphate in the preparation of the nonaqueous electrolytic solution of Example 11. The cycle test and the gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 70%, and the amount of gas generated after continuous charging was as small as 1.23 mL.
[実施例13]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレン(3−ブテニル)フォスフェートを用いた以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は76%と高く、連続充電後発生ガス量は1.14mLと少なかった。
[Example 13]
A sheet-like battery was prepared in the same manner as in Example 11 except that ethylene (3-butenyl) phosphate was used instead of ethylene (3-butynyl) phosphate in the preparation of the nonaqueous electrolytic solution of Example 11. The cycle test and the gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 76%, and the amount of gas generated after continuous charging was as small as 1.14 mL.
[実施例14]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレンヘキシルホスホネートを用いた以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は69%と高く、連続充電後発生ガス量は1.31mLと少なかった。
[Example 14]
In the preparation of the nonaqueous electrolytic solution of Example 11, a sheet-like battery was prepared in the same manner as in Example 11 except that ethylenehexylphosphonate was used instead of ethylene (3-butynyl) phosphate, and the above cycle test and A gas generation test was conducted. As a result, the capacity retention rate after 100 cycles was as high as 69%, and the amount of gas generated after continuous charging was as small as 1.31 mL.
[実施例15]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートの代わりに、エチレンオクチルフォスフェートを用いた以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は71%と高く、連続充電後発生ガス量は1.27mLと少なかった。
[Example 15]
In the preparation of the nonaqueous electrolytic solution of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that ethylene octyl phosphate was used instead of ethylene (3-butynyl) phosphate, and the above cycle test was performed. And a gas generation test was conducted. As a result, the capacity retention rate after 100 cycles was as high as 71%, and the amount of gas generated after continuous charging was as small as 1.27 mL.
[実施例16]
実施例11の非水電解液の調製において、混合溶媒に、さらにLiBF4を0.5質量%添加した以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は75%と高く、連続充電後発生ガス量は1.15mLと少なかった。
[Example 16]
In the preparation of the nonaqueous electrolytic solution of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that 0.5% by mass of LiBF 4 was further added to the mixed solvent, and the above cycle test and gas generation test were performed. Went. As a result, the capacity retention rate after 100 cycles was as high as 75%, and the amount of gas generated after continuous charging was as small as 1.15 mL.
[実施例17]
実施例11の非水電解液の調製において、LiB(C2O4)2の代わりに、LiPF2(C2O4)2を用いた以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は72%と高く、連続充電後発生ガス量は1.18mLと少なかった。
[Example 17]
A sheet-like battery was produced in the same manner as in Example 11 except that LiPF 2 (C 2 O 4 ) 2 was used instead of LiB (C 2 O 4 ) 2 in the preparation of the nonaqueous electrolytic solution of Example 11. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 72%, and the amount of gas generated after continuous charging was as small as 1.18 mL.
[実施例18]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートを0.3質量%添加する代わりに、1質量%添加した以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は73%と高く、連続充電後発生ガス量は1.09mLと少なかった。
[Example 18]
In the preparation of the nonaqueous electrolytic solution of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that 1% by mass was added instead of 0.3% by mass of ethylene (3-butynyl) phosphate. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 73%, and the amount of gas generated after continuous charging was as low as 1.09 mL.
[実施例19]
実施例11の非水電解液の調製において、エチレン(3−ブチニル)フォスフェートを0.3質量%添加する代わりに、3質量%添加した以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は68%と高く、連続充電後発生ガス量は1.01mLと少なかった。
[Example 19]
In the preparation of the nonaqueous electrolytic solution of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that 3% by mass was added instead of 0.3% by mass of ethylene (3-butynyl) phosphate. The above cycle test and gas generation test were conducted. As a result, the capacity retention rate after 100 cycles was as high as 68%, and the amount of gas generated after continuous charging was as low as 1.01 mL.
[比較例8]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は32%と低く、連続充電後発生ガス量は4.32mLと多かった。
[Comparative Example 8]
12.1% by mass of LiPF 6 was added to a mixed solvent obtained by mixing ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 1: 2 to obtain a nonaqueous electrolytic solution. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 32%, and the amount of gas generated after continuous charging was as large as 4.32 mL.
[比較例9]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は64%と低く、連続充電後発生ガス量は2.62mLと多かった。
[Comparative Example 9]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 2, LiPF 6 is 12.1% by mass, LiB (C 2 O 4 ) 2 is 1% by mass, Was added to obtain a non-aqueous electrolyte. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 64%, and the amount of gas generated after continuous charging was as large as 2.62 mL.
[比較例10]
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)とを体積比1:2で混合した混合溶媒に、エチレン(3−ブチニル)フォスフェートを0.3質量%と、LiPF6を12.1質量%と、を添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は52%と低く、連続充電後発生ガス量は1.38mLと多かった。
[Comparative Example 10]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, ethylene (3-butynyl) phosphate was 0.3% by mass, and LiPF 6 was 12.1% by mass. To make a non-aqueous electrolyte. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 52%, and the amount of gas generated after continuous charging was as high as 1.38 mL.
[比較例11]
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)とを体積比1:2で混合した混合溶媒に、LiPF6を12.1質量%と、LiBF4を0.5質量%と、LiB(C2O4)2を1質量%と、を添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は65%と低く、連続充電後発生ガス量は2.61mLと多かった。
[Comparative Example 11]
In a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 2, LiPF 6 was 12.1% by mass, LiBF 4 was 0.5% by mass, and LiB (C 2 1 mass% of O 4 ) 2 was added to make a non-aqueous electrolyte. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 65%, and the amount of gas generated after continuous charging was as large as 2.61 mL.
[比較例12]
エチレンカーボネート(EC)とジメチルカーボネート(DMC)と2,2,2−トリフルオロエチルエチレンフォスフェートを体積比42.5:42.5:15で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は50%と低く、連続充電後発生ガス量は1.32mLと多かった。
[Comparative Example 12]
12.1 mass of LiPF 6 in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC) and 2,2,2-trifluoroethyl ethylene phosphate were mixed at a volume ratio of 42.5: 42.5: 15 % To make a non-aqueous electrolyte. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity maintenance rate after 100 cycles was as low as 50%, and the amount of gas generated after continuous charging was as large as 1.32 mL.
[比較例13]
2−メトキシ−1,3,2−ジオキサフォスフォラン−2−オキサイドとジエチルカーボネート(DEC)を体積比1:1で混合した混合溶媒に、LiPF6を12.1質量%添加して非水電解液とした。実施例11の試験用電池の作製において、上記非水電解液を用いたこと以外、実施例11と同様にしてシート状電池を作製し、上記サイクル試験及びガス発生試験を行った。その結果、100サイクル後容量維持率は4%と非常に低く、連続充電後発生ガス量は2.21mLと多かった。
[Comparative Example 13]
To a mixed solvent in which 2-methoxy-1,3,2-dioxaphosphorane-2-oxide and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 1, 12.1% by mass of LiPF 6 was added and non-aqueous. An electrolyte was used. In the production of the test battery of Example 11, a sheet-like battery was produced in the same manner as in Example 11 except that the non-aqueous electrolyte was used, and the cycle test and the gas generation test were performed. As a result, the capacity retention rate after 100 cycles was as low as 4%, and the amount of gas generated after continuous charging was as large as 2.21 mL.
以上の実施例11〜19、及び比較例8〜13で得られた結果を、表2に示す。表2から、実施例11〜19のリチウムイオン二次電池はいずれも、環状リン酸エステル(A)を含まない非水電解液を用いた比較例9及び11、シュウ酸構造を有するリチウム塩化合物(C)を含まない非水電解液を用いた比較例10と比して、サイクル特性が向上し、ガス発生量が大幅に低減していることが明らかとなった。以上より、本実施形態の効果は、非水電解液中に環状リン酸エステル(A)とシュウ酸構造を有するリチウム塩化合物(C)を共存させた場合に、特有の効果であることが示された。 Table 2 shows the results obtained in Examples 11 to 19 and Comparative Examples 8 to 13. From Table 2, the lithium ion secondary batteries of Examples 11 to 19 are all Comparative Examples 9 and 11 using a nonaqueous electrolytic solution containing no cyclic phosphate (A), lithium salt compounds having an oxalic acid structure As compared with Comparative Example 10 using a non-aqueous electrolyte not containing (C), it was revealed that the cycle characteristics were improved and the gas generation amount was greatly reduced. From the above, it is shown that the effect of the present embodiment is a unique effect when the cyclic phosphate ester (A) and the lithium salt compound (C) having an oxalic acid structure coexist in the nonaqueous electrolytic solution. It was done.
また、実施例11〜19のリチウムイオン二次電池はいずれも、特許文献3に記載されている2,2,2−トリフルオロエチルエチレンフォスフェートを非水溶媒に対して15体積%含有させた比較例12、特許文献4に記載されている2−メトキシ−1,3,2−ジオキサフォスフォラン−2−オキサイドを非水溶媒に対して50体積%含有させた比較例13と比して、サイクル特性が大幅に向上し、ガス発生量が低減していることが明確となった。 In addition, all of the lithium ion secondary batteries of Examples 11 to 19 contained 15% by volume of 2,2,2-trifluoroethylethylene phosphate described in Patent Document 3 with respect to the nonaqueous solvent. Compared to Comparative Example 13 and Comparative Example 13 containing 50% by volume of 2-methoxy-1,3,2-dioxaphosphorane-2-oxide described in Patent Document 4 with respect to the non-aqueous solvent It was clarified that the cycle characteristics were greatly improved and the gas generation amount was reduced.
本発明の非水電解液を用いたリチウムイオン二次電池は、各種民生機器用電源、自動車用電源への産業上利用可能性を有する。 The lithium ion secondary battery using the non-aqueous electrolyte of the present invention has industrial applicability to various consumer equipment power supplies and automobile power supplies.
Claims (7)
シュウ酸構造を有さないリチウム塩化合物(B)と、
シュウ酸構造を有するリチウム塩化合物(C)と、
非水溶媒と、を含有し、
前記環状リン酸エステル化合物(A)の含有量が、前記非水電解液の総量に対して、0.01質量%以上10質量%以下である、非水電解液。 A cyclic phosphate compound (A) represented by the following general formula (1);
A lithium salt compound (B) having no oxalic acid structure;
A lithium salt compound (C) having an oxalic acid structure;
A non-aqueous solvent ,
A nonaqueous electrolytic solution in which the content of the cyclic phosphate compound (A) is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the nonaqueous electrolytic solution.
前記リチウム塩化合物(C)の含有量が、前記非水電解液の総量に対して、0.01質量%以上10質量%以下である、請求項1に記載の非水電解液。 The content of the lithium salt compound (B) is 3% by mass or more and 30% by mass or less with respect to the total amount of the non-aqueous electrolyte,
The content of the lithium salt compound (C), the total amount of the non-aqueous electrolyte, 10 mass% or less than 0.01 mass%, non-aqueous electrolyte according to claim 1.
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