WO2011004483A1 - ポリマーゲル電解質及びそれを用いたポリマー二次電池 - Google Patents
ポリマーゲル電解質及びそれを用いたポリマー二次電池 Download PDFInfo
- Publication number
- WO2011004483A1 WO2011004483A1 PCT/JP2009/062531 JP2009062531W WO2011004483A1 WO 2011004483 A1 WO2011004483 A1 WO 2011004483A1 JP 2009062531 W JP2009062531 W JP 2009062531W WO 2011004483 A1 WO2011004483 A1 WO 2011004483A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- group
- secondary battery
- general formula
- lithium
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 98
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 26
- -1 cyclic sulfonate ester Chemical class 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 6
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000000457 gamma-lactone group Chemical group 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 125000001153 fluoro group Chemical class F* 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 10
- 230000008961 swelling Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000011267 electrode slurry Substances 0.000 description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910000733 Li alloy Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000001989 lithium alloy Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- RSHKWPIEJYAPCL-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1(CC)COC1 RSHKWPIEJYAPCL-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- VFRGATWKSPNXLT-UHFFFAOYSA-N 1,2-dimethoxybutane Chemical compound CCC(OC)COC VFRGATWKSPNXLT-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BEKPOUATRPPTLV-UHFFFAOYSA-N [Li].BCl Chemical compound [Li].BCl BEKPOUATRPPTLV-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Definitions
- the present invention relates to a polymer gel electrolyte and a polymer secondary battery using the same.
- Polymer secondary batteries such as lithium polymer batteries can be thinned, have a high degree of freedom in shape selection, and have high safety by not using an electrolyte. Attention has been paid. With the recent increase in functions of mobile devices, higher energy and the accompanying improvements in battery characteristics have become the goal of technological development of lithium polymer batteries.
- Patent Document 1 describes that cycle characteristics are improved by using a gel electrolyte containing a physical crosslinkable polymer and a chemical crosslinkable polymer.
- Patent Document 2 describes that the impregnation property of the pregel solution is improved by surface modification of the separator to be used.
- Patent Document 3 discloses a lithium polymer that has excellent battery performance and high safety by gelling an electrolyte with a crosslinkable material and using a non-conductive porous material and electrically insulating particles as a separator. It is described that it becomes a battery.
- Non-Patent Document 1 discusses electrode materials and cell shapes in polymer secondary batteries using gel electrolytes. For example, although it is expensive as negative electrode material, artificial graphite (bulk graphite) is used. Therefore, it is described that the expansion of the cell is suppressed and the cycle characteristics are improved.
- artificial graphite bulk graphite
- the polymer secondary battery using the gel electrolyte is generally inferior in cycle characteristics to the secondary battery using the electrolytic solution.
- the polymer secondary battery has a large internal resistance during high-temperature storage and high-temperature cycles, and does not have sufficient characteristics as a battery applied to an electric vehicle, a battery for power storage, and the like.
- the present invention has been made in view of the above problems. That is, the subject of this invention suppresses the swelling of the cell in a polymer secondary battery, and improves cycling characteristics and high temperature storage characteristics.
- an aprotic solvent, a supporting salt, a cyclic sulfonic acid ester having at least two sulfonyl groups, and a methacrylic acid ester polymerization represented by the following general formula (1)
- a polymer gel electrolyte comprising a crosslinked product obtained by crosslinking a product.
- the polymer secondary battery containing a positive electrode, a negative electrode, and the said polymer gel electrolyte is provided.
- n satisfies 1800 ⁇ n ⁇ 3000
- m satisfies 350 ⁇ m ⁇ 600.
- cell swelling in a polymer secondary battery can be suppressed, and cycle characteristics and high-temperature storage characteristics can be improved.
- the polymer gel electrolyte according to the present invention is obtained by crosslinking an aprotic solvent, a supporting salt, a cyclic sulfonic acid ester having at least two sulfonyl groups, and a methacrylic acid ester polymer represented by the general formula (1). And a crosslinked product.
- a mixture of an aprotic solvent and a supporting salt is referred to as an electrolytic solution.
- the polymer electrolyte is used for a polymer secondary battery, and is particularly preferably used for a lithium polymer secondary battery.
- aprotic solvent examples include cyclic carbonates such as propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), and vinylene carbonate (VC); dimethyl carbonate (DMC) and diethyl carbonate (DEC).
- PC propylene carbonate
- EC ethylene carbonate
- BC butylene carbonate
- VC vinylene carbonate
- DMC dimethyl carbonate
- DEC diethyl carbonate
- Chain carbonates such as ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC); aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate; ⁇ -lactones such as ⁇ -butyrolactone; , 2-ethoxyethane (DEE), chain ethers such as ethoxymethoxyethane (EME); cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran; fluorine derivatives thereof; dimethyl sulfoxide, 1,3-dioxolane, Formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-d
- the supporting salt can be appropriately selected from substances that can increase the conductivity of the aprotic solvent in consideration of the type of the polymer secondary battery.
- a supporting salt LiPF 6, LiAsF 6, LiAlCl 4, LiClO 4, LiBF 4, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , lithium carboxylate, lithium chloroborane, lithium tetraphenylborate, LiBr, LiI, LiSCN, LiCl, LiF Etc.
- the supporting salt may be one kind or two or more kinds.
- the concentration of the supporting salt in the electrolytic solution is preferably 5 to 25% by mass. If the concentration of the supporting salt is 5% by mass or more, a desired ionic conductivity can be achieved. If the concentration of the supporting salt is 25% by mass or less, a decrease in ionic conductivity due to an increase in the viscosity of the electrolyte can be suppressed.
- a cyclic sulfonic acid ester having at least two sulfonyl groups (hereinafter simply referred to as “cyclic sulfonic acid ester”) is a component that contributes to the formation of a passive film at the electrode interface of a polymer secondary battery. Decomposition of solvent molecules can be suppressed. Further, when the positive electrode active material is an oxide containing manganese, the cyclic sulfonate ester has an effect of suppressing the elution of manganese or preventing the eluted manganese from adhering to the negative electrode.
- cyclic sulfonic acid ester examples include compounds represented by the general formula (2).
- Q represents an oxygen atom, a methylene group or a single bond
- A represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a carbonyl group, a sulfinyl group, a substituted or unsubstituted carbon.
- B is a substituted or unsubstituted alkylene group, a substituted or An unsubstituted fluoroalkylene group or an oxygen atom is shown.
- Q when Q is a single bond, the carbon molecule constituting A and S form a CS single bond.
- the carbon number of A indicates the number of carbons constituting the ring, and does not include the number of carbons contained in the side chain.
- A is a substituted or unsubstituted fluoroalkylene group having 1 to 6 carbon atoms
- A may have a methylene unit and a fluoromethylene unit, or may have only a fluoromethylene unit.
- an alkylene unit or a fluoroalkylene unit is bonded via an ether bond, the alkylene units may be bonded, the fluoroalkylene units may be bonded, or the alkylene unit and the fluoroalkylene. Units may be combined.
- the compound represented by the general formula (2) can be produced by the method described in Patent Document 4.
- Specific examples of the compound represented by the general formula (2) include cyclic disulfonic acid esters represented by the general formulas (3) to (8).
- x is 0 or 1
- n is an integer of 1 to 5
- R represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom.
- x is 0 or 1
- n is an integer of 1 to 5
- R represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom.
- x is 0 or 1
- m is independently 1 or 2
- n is an integer of 1 or more and 4 or less
- R is a hydrogen atom, a methyl group, an ethyl group or a halogen. Indicates an atom.
- x is 0 or 1
- m is independently 1 or 2
- n is an integer of 1 or more and 4 or less
- R is a hydrogen atom, a methyl group, an ethyl group or a halogen. Indicates an atom.
- x is 0 or 1
- m is independently 1 or 2
- n is an integer of 1 or more and 4 or less
- R is a hydrogen atom, a methyl group, an ethyl group or a halogen. Indicates an atom.
- x is 0 or 1
- m is independently 1 or 2
- n is an integer of 1 or more and 4 or less
- R is a hydrogen atom, a methyl group, an ethyl group or a halogen. Indicates an atom.
- the cyclic sulfonic acid ester may be one kind or two or more kinds.
- the mixing amount of the cyclic sulfonic acid ester is preferably 0.005 to 10% by mass and more preferably 0.01 to 5% by mass with respect to 100% by mass of the electrolytic solution.
- the mixing amount of the cyclic sulfonic acid ester is preferably 0.005 to 10% by mass and more preferably 0.01 to 5% by mass with respect to 100% by mass of the electrolytic solution.
- the methacrylic acid ester polymer represented by the general formula (1) is obtained by radical copolymerization of methyl methacrylate and (3-ethyl-3-oxetanyl) methyl methacrylate.
- N representing the number of methyl methacrylate units satisfies 1800 ⁇ n ⁇ 3000
- m representing the number of (3-ethyl-3-oxetanyl) methyl methacrylate units satisfies 350 ⁇ m ⁇ 600.
- the methacrylic acid ester polymer represented by the general formula (1) may be a block copolymer or a random copolymer.
- N and m represent average values and may not be integers.
- a crosslinked product obtained by crosslinking the methacrylic acid ester polymer represented by the general formula (1) is an oxetanyl group possessed by the methacrylic acid ester polymer represented by the general formula (1).
- the cationic polymerization initiator generally known polymerization initiators can be used.
- the use of a small amount of an acidic substance obtained by hydrolyzing the lithium salt and the anion component of the lithium salt contained in the electrolytic solution is useful for the battery.
- the characteristic to give is small and preferable.
- the content of the lithium salt in the electrolytic solution is the same as the preferred concentration of the supporting salt in the electrolytic solution.
- the mixing amount of the crosslinked body is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and more preferably 1.5 to 2.5% by mass with respect to 100% by mass of the electrolytic solution. More preferably.
- gelation capable of favorably holding the electrolytic solution can be achieved.
- the polymer electrolyte according to the present invention includes, for example, a step of dissolving a supporting salt in an aprotic solvent, a step of dissolving a cyclic sulfonic acid ester in an aprotic solvent, and a general formula (1) in an aprotic solvent.
- the use of the polymer electrolyte according to the present invention for a polymer secondary battery can suppress cell swelling and improve cycle characteristics and high temperature storage characteristics.
- the polymer secondary battery according to the present invention includes a positive electrode, a negative electrode, and the polymer gel electrolyte.
- the positive electrode it is possible to use a positive electrode active material layer formed on a current collector made of metal such as aluminum foil.
- the positive electrode active material layer can be formed by applying and drying a positive electrode slurry on a current collector and then compressing and molding the positive electrode slurry.
- the positive electrode slurry is obtained by dispersing and kneading a positive electrode active material in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a conductive auxiliary material such as carbon black and a binder such as polyvinylidene fluoride (PVDF). be able to.
- NMP N-methyl-2-pyrrolidone
- PVDF polyvinylidene fluoride
- a lithium-containing composite oxide such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 can be used. Further, the transition metal portion of these lithium-containing composite oxides may be replaced with another element. Alternatively, a lithium-containing composite oxide having a plateau at 4.5 V or more at the metal lithium counter electrode potential can be used. Specific examples of such lithium-containing composite oxides include spinel-type lithium manganese composite oxides, olivine-type lithium-containing composite oxides, and reverse spinel-type lithium-containing composite oxides. Specifically, for example, the compound represented by the general formula (9) is applicable.
- x satisfies 0 ⁇ x ⁇ 2
- a satisfies 0 ⁇ a ⁇ 1.2
- M is selected from the group consisting of Ni, Co, Fe, Cr, and Cu. Is at least one kind.
- a negative electrode having a negative electrode active material layer formed on a current collector made of a metal such as copper foil can be used.
- the negative electrode active material in addition to lithium metal or lithium alloy, one or more substances selected from materials capable of inserting and extracting lithium can be used. Specific examples of the material that can occlude and release lithium include carbon materials and oxides.
- the lithium alloy is composed of lithium and a metal capable of forming an alloy with lithium.
- a binary or ternary alloy of lithium and a metal such as Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, and La Is mentioned.
- the lithium metal or lithium alloy is preferably in an amorphous state. This is because the amorphous structure hardly causes deterioration due to non-uniformity such as crystal grain boundaries and defects.
- the negative electrode active material layer made of lithium metal or lithium alloy can be melt cooling, liquid quenching, atomizing, vacuum deposition, sputtering, plasma CVD, photo CVD, thermal CVD, sol-gel, etc. It can be formed by a method.
- the carbon material graphite, amorphous carbon, diamond-like carbon, carbon nanotube, or a composite oxide thereof can be used. Of these, graphite or amorphous carbon is preferable.
- graphite has high electron conductivity, excellent adhesion to a current collector made of a metal such as copper, and voltage flatness. Since it is formed at a high processing temperature, it contains few impurities and improves negative electrode performance. Works in an advantageous manner.
- the negative electrode active material layer containing a carbon material as a negative electrode active material can be formed by applying and drying a negative electrode slurry containing a carbon material on a current collector, followed by compression and molding.
- the negative electrode slurry can be obtained by dispersing and kneading a carbon material as a negative electrode active material in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a binder such as polyvinylidene fluoride (PVDF).
- NMP N-methyl-2-pyrrolidone
- PVDF polyvinylidene fluoride
- silicon oxide silicon oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, or a composite thereof can be used.
- silicon oxide is preferable because it is stable and does not cause a reaction with other compounds.
- the oxide is preferably in an amorphous state because deterioration due to nonuniformity such as crystal grain boundaries and defects does not occur.
- the negative electrode active material layer made of an oxide can be formed by a method such as vapor deposition, CVD, or sputtering.
- the polymer secondary battery can be manufactured as follows. First, a positive electrode and a negative electrode are stacked via a separator to form a laminate. Or after winding a positive electrode and a negative electrode flatly via a separator, it shape
- separator those generally used in lithium polymer batteries such as nonwoven fabric and polyolefin microporous membrane can be used.
- the separator is not essential, and the polymer gel electrolyte can have a separator function.
- the polymer secondary battery according to the present invention is suppressed in cell swelling and has excellent cycle characteristics and high-temperature storage characteristics. That is, by applying the present invention to a polymer secondary battery composed of a laminate film outer package, it is possible to suppress resistance increase and battery swelling (gas generation). The effect is remarkable in the secondary battery.
- Example 1 First, the production of the positive electrode 1 will be described with reference to FIG. N-methyl-2 was mixed with 85% by mass of LiMn 2 O 4 as a positive electrode active material, 7% by mass of acetylene black as a conductive auxiliary material, and 8% by mass of polyvinylidene fluoride as a binder.
- a positive electrode slurry was prepared by adding pyrrolidone and further mixing. This positive electrode slurry is applied to both surfaces of a 20 ⁇ m thick Al foil 2 as a current collector by a doctor blade method so that the thickness after the roll press treatment is 160 ⁇ m, thereby forming a positive electrode active material application portion 3. did.
- a positive electrode active material non-applied portion 4 that is not coated with a positive electrode active material on both sides is provided at one end, and a positive electrode active material that is coated with a positive electrode active material only on one side is provided at the other end.
- a substance single-side application unit 5 is provided.
- the positive electrode conductive tab 6 was attached to the positive electrode active material non-application part 4, and it was set as the positive electrode 1.
- a negative electrode slurry was prepared by adding N-methylpyrrolidone to a mixture of 90% by mass of flaky graphite as a negative electrode active material and 10% by mass of polyvinylidene fluoride as a binder and further mixing them. This negative electrode slurry was applied to both surfaces of a 10 ⁇ m-thick Cu foil 8 serving as a current collector so that the thickness after the roll press treatment was 120 ⁇ m, thereby forming a negative electrode active material application part 9.
- one end is provided with a negative electrode active material non-applied portion 11 that is not coated with a negative electrode active material on both surfaces, and a negative electrode active material single-sided coated portion 10 that is coated with a negative electrode active material only on one side.
- the negative electrode conductive tab 12 was attached to the negative electrode active material non-application part 11, and it was set as the negative electrode 7.
- the production of the battery element will be described with reference to FIG.
- Two separators 13 made of polyethylene having a film thickness of 12 ⁇ m and a porosity of 35% are welded and cut, and the cut portion is fixed to the winding core of the winding device and wound up.
- the positive electrode 1 and the negative electrode 7 are respectively arranged such that the side where the positive electrode conductive tab 6 and the negative electrode conductive tab 8 are not attached is the tip side, the negative electrode is disposed between the two separators, and the positive electrode is disposed on the upper surface of the separator.
- the battery element hereinafter referred to as jelly roll (J / R) was formed by rotating and winding. At this stage, the gel electrolyte 14 of FIG. 3 does not exist.
- This J / R was accommodated in an embossed laminate outer package 15 as shown in FIG. 4, the sides of the laminate outer package 15 were folded back, and heat fusion was performed leaving a portion for injecting the pregel solution.
- the obtained lithium polymer battery was charged to a voltage of 4.2 V (charging conditions: current 0.2 C, time 6.5 h, temperature 20 ° C.), and then discharged to a voltage 3.0 V at 0.2 C.
- the discharge capacity at that time was defined as the initial capacity.
- the charging conditions were an upper limit voltage of 4.2 V, a current of 1 C, and a time of 2.5 h, and the discharging conditions were a lower limit voltage of 3.0 V and a current of 1 C. All charging / discharging was implemented at 40 degreeC. And the ratio of the discharge capacity (1C) of the 500th cycle with respect to the discharge capacity (1C) of the 1st cycle was made into the capacity
- Example 2 Compound No.
- a lithium polymer battery was produced in the same manner as in Example 1 except that the compound represented by 1 was changed to the compound shown in Table 2.
- Table 2 shows the characteristics of the obtained lithium polymer battery.
- the lithium polymer batteries produced in Examples 1 to 4 are Comparative Example 1 in which no cyclic sulfonic acid ester was used, and Comparative Example 2 in which VC was used in place of the cyclic sulfonic acid ester.
- the capacity retention rate after 500 cycles is greatly improved, and the volume change after 500 cycles is also greatly suppressed.
- Example 5 As an electrolyte for preparing a pregel solution using amorphous carbon as the negative electrode active material, 20% by mass of propylene carbonate (PC), 21% by mass of ethylene carbonate (EC), and 47% by mass of diethyl carbonate (DEC) A lithium polymer battery was produced in the same manner as in Example 1 except that an electrolyte solution in which LiPF 6 as a supporting salt of 12% by mass was added to an aprotic solvent consisting of Table 3 shows the characteristics of the obtained lithium polymer battery.
- PC propylene carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- Example 6 Compound No.
- a lithium polymer battery was produced in the same manner as in Example 5 except that the compound represented by 1 was changed to the compound shown in Table 3.
- Table 3 shows the characteristics of the obtained lithium polymer battery.
- the lithium polymer batteries produced in Examples 5 to 8 were Comparative Example 3 in which no cyclic sulfonic acid ester was used, and Comparative Example 4 in which VC was used in place of the cyclic sulfonic acid ester.
- the capacity retention rate after 500 cycles is greatly improved, and the volume change after 500 cycles is also greatly suppressed.
- Example 9 A lithium polymer battery was produced in the same manner as in Example 1, and the direct current resistance value of the lithium polymer battery when stored in a fully charged state was measured.
- the prepared lithium polymer battery was charged (upper limit voltage 4.2 V) and discharged (lower limit voltage 3.0 V) at 20 ° C. once.
- the charging current and discharging current at this time are constant (1C), the discharging capacity at this time is defined as the initial capacity, and the resistance at that time is defined as the initial resistance.
- the battery was charged with a constant current (1C) to a predetermined voltage (4.2 V) for 2.5 hours, and then allowed to stand at 20 ° C., 45 ° C. and 60 ° C. for 90 days.
- Example 10 to 12 Compound No. A lithium polymer battery was produced in the same manner as in Example 9, except that the compound represented by 1 was changed to the compound shown in Table 4, and the same evaluation as in Example 9 was performed. Table 4 shows the obtained results.
- the lithium polymer batteries produced in Examples 9 to 12 were Comparative Example 5 in which no cyclic sulfonic acid ester was used, and Comparative Example 6 in which VC was used instead of the cyclic sulfonic acid ester. It was found that the rate of increase in resistance at each temperature was greatly suppressed as compared with the prepared lithium polymer battery. In particular, the suppression of increase in resistance at 60 ° C. storage was significant.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明に係るポリマーゲル電解質は、非プロトン性溶媒と、支持塩と、少なくともスルホニル基を2個有する環式スルホン酸エステルと、一般式(1)で示されるメタクリル酸エステル重合物を架橋させてなる架橋体とを含んでいる。なお、本明細書において、非プロトン性溶媒及び支持塩の混合物を電解液と呼ぶ。このポリマー電解質は、ポリマー二次電池に用いられるが、特にリチウムポリマー二次電池に用いられることが好ましい。
本発明に係るポリマー二次電池は、正極と、負極と、上記のポリマーゲル電解質とを含み構成される。
一般式(9)において、xは0<x<2を満たし、aは0<a<1.2を満たし、Mは、Ni、Co、Fe、Cr及びCuからなる群より選択された選択される少なくとも一種である。
まず、図1により、正極1の作製について説明する。85質量%の正極活物質としてのLiMn2O4と、7質量%の導電補助材としてのアセチレンブラックと、8質量%のバインダーとしてのポリフッ化ビニリデンとを混合したものに、N-メチル-2-ピロリドンを加えてさらに混合することで、正極スラリーを調製した。この正極スラリーを、ドクターブレード法により、集電体となる厚さ20μmのAl箔2の両面に、ロールプレス処理後の厚さが160μmになるように塗布し、正極活物質塗布部3を形成した。ただし、一方の端部には、両面とも正極活物質が塗布されていない正極活物質非塗布部4が設けられており、他方の端部には、片面のみ正極活物質が塗布された正極活物質片面塗布部5が設けられている。そして、その正極活物質非塗布部4に正極導電タブ6を取り付けて、正極1とした。
化合物No.1で示される化合物を、表2に示す化合物に変更したこと以外は、実施例1と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表2に示す。
化合物No.1で示される化合物を用いなかったこと以外は、実施例1と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表2に示す。
化合物No.1で示される化合物をVCに変更したこと以外は、実施例1と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表2に示す。
負極活物質として非晶質炭素を用い、プレゲル溶液を調製するための電解液として、20質量%のプロピレンカーボネート(PC)と21質量%のエチレンカーボネート(EC)と47質量%のジエチルカーボネート(DEC)とからなる非プロトン性溶媒に、12質量%の支持塩としてのLiPF6とを添加した電解液を用いたこと以外は、実施例1と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表3に示す。
化合物No.1で示される化合物を、表3に示す化合物に変更したこと以外は、実施例5と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表3に示す。
化合物No.1で示される化合物を用いなかったこと以外は、実施例5と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表3に示す。
化合物No.1で示される化合物をVCに変更したこと以外は、実施例5と同様にしてリチウムポリマー電池を作製した。得られたリチウムポリマー電池の特性を表3に示す。
実施例1と同様にしてリチウムポリマー電池を作製し、満充電状態での保存放置におけるリチウムポリマー電池の直流抵抗値を測定した。
化合物No.1で示される化合物を、表4に示す化合物に変更したこと以外は、実施例9と同様にしてリチウムポリマー電池を作製し、実施例9と同様の評価を行った。得られた結果を表4に示す。
化合物No.1で示される化合物を用いなかったこと以外は、実施例9と同様にしてリチウムポリマー電池を作製し、実施例9と同様の評価を行った。得られた結果を表4に示す。
化合物No.1で示される化合物をVCに変更したこと以外は、実施例9と同様にしてリチウムポリマー電池を作製し、実施例9と同様の評価を行った。得られた結果を表4に示す。
2 Al箔
3 正極活物質塗布部
4 正極活物質非塗布部
5 正極活物質片面塗布部
6 正極導電タブ
7 負極
8 Cu箔
9 負極活物質塗布部
10 負極活物質片面塗布部
11 負極活物質非塗布部
12 負極導電タブ
13 セパレーター
14 ポリマーゲル電解質
15 ラミネート外装体
Claims (8)
- 前記非プロトン性溶媒として、環状カーボネート類、鎖状カーボネート類、脂肪族カルボン酸エステル類、γ-ラクトン類、環状エーテル類、鎖状エーテル類及びそれらのフッ素誘導体からなる群より選択された溶媒を含む請求項1又は2に記載のポリマーゲル電解質。
- 前記支持塩として、LiPF6、LiBF4、LiAsF6及びLiSbF6からなる群より選択された物質を含む請求項1~3のいずれかに記載のポリマーゲル電解質。
- 正極と、負極と、請求項1~4のいずれかに記載のポリマーゲル電解質とを含むポリマー二次電池。
- 前記正極が、正極活物質として、リチウム含有複合酸化物を含む請求項5に記載のポリマー二次電池。
- 前記負極が、負極活物質として、リチウムを吸蔵・放出できる材料からなる群より選択される物質を含む請求項5又は6に記載のポリマー二次電池。
- 前記リチウムを吸蔵・放出できる材料が、炭素材料である請求項7に記載のポリマー二次電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011521748A JPWO2011004483A1 (ja) | 2009-07-09 | 2009-07-09 | ポリマーゲル電解質及びそれを用いたポリマー二次電池 |
US13/382,851 US20120115037A1 (en) | 2009-07-09 | 2009-07-09 | Polymer gel electrolyte and polymer secondary battery using same |
CN200980160379XA CN102473966A (zh) | 2009-07-09 | 2009-07-09 | 聚合物凝胶电解质和使用它的聚合物二次电池 |
PCT/JP2009/062531 WO2011004483A1 (ja) | 2009-07-09 | 2009-07-09 | ポリマーゲル電解質及びそれを用いたポリマー二次電池 |
EP09847085.9A EP2453511A4 (en) | 2009-07-09 | 2009-07-09 | POLYMER GEL ELECTROLYTE AND POLYMER ACCUMULATOR THEREWITH |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2009/062531 WO2011004483A1 (ja) | 2009-07-09 | 2009-07-09 | ポリマーゲル電解質及びそれを用いたポリマー二次電池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011004483A1 true WO2011004483A1 (ja) | 2011-01-13 |
Family
ID=43428921
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/062531 WO2011004483A1 (ja) | 2009-07-09 | 2009-07-09 | ポリマーゲル電解質及びそれを用いたポリマー二次電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20120115037A1 (ja) |
EP (1) | EP2453511A4 (ja) |
JP (1) | JPWO2011004483A1 (ja) |
CN (1) | CN102473966A (ja) |
WO (1) | WO2011004483A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8802283B2 (en) * | 2012-01-19 | 2014-08-12 | Samsung Sdi Co., Ltd. | Fabricating method of secondary battery |
WO2016125726A1 (ja) * | 2015-02-05 | 2016-08-11 | 日立マクセル株式会社 | リチウム二次電池 |
US9899703B2 (en) | 2013-03-01 | 2018-02-20 | Nec Corporation | Gel electrolyte and polymer secondary battery using same |
WO2018150567A1 (ja) * | 2017-02-20 | 2018-08-23 | 日本電気株式会社 | リチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池 |
JP7047181B1 (ja) | 2021-12-15 | 2022-04-04 | 第一工業製薬株式会社 | 非水電解液およびリチウムイオン二次電池 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3211707B1 (en) * | 2014-10-21 | 2019-12-04 | Nec Corporation | Secondary battery and production method therefor |
CN107579280B (zh) * | 2016-12-14 | 2019-09-06 | 广州天赐高新材料股份有限公司 | 含环状二磺酸硅基酯的锂二次电池电解液和锂二次电池 |
US20200028212A1 (en) * | 2017-03-15 | 2020-01-23 | Envision Aesc Energy Devices Ltd. | Lithium ion secondary battery |
CN114221036B (zh) * | 2021-12-14 | 2023-11-28 | 珠海冠宇电池股份有限公司 | 一种电解液及包括该电解液的电化学装置 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1985003075A1 (en) | 1984-01-16 | 1985-07-18 | Cronyn Marshall W | Cancer chemotherapeutic cyclic and acyclic disulfonic ester compounds, method of use therefor, and intermediates |
JP2002100406A (ja) | 2000-09-25 | 2002-04-05 | Toshiba Battery Co Ltd | ポリマーリチウム二次電池及びその製造方法 |
JP2002110245A (ja) * | 2000-10-03 | 2002-04-12 | Maxell Hokuriku Seiki Kk | ポリマー固体電解質リチウムイオン2次電池 |
JP2003257490A (ja) | 2002-02-28 | 2003-09-12 | Mitsubishi Materials Corp | ゲル状ポリマー電解質及びそれを用いたリチウムポリマー電池 |
JP2005310445A (ja) * | 2004-04-19 | 2005-11-04 | Hitachi Maxell Ltd | ゲル状電解質およびそれを用いた電気化学素子 |
JP2007273445A (ja) * | 2006-03-09 | 2007-10-18 | Nec Tokin Corp | ポリマーゲル電解質およびそれを用いたポリマー二次電池 |
JP2009070605A (ja) | 2007-09-11 | 2009-04-02 | Dai Ichi Kogyo Seiyaku Co Ltd | リチウムポリマー電池 |
JP2009140641A (ja) * | 2007-12-04 | 2009-06-25 | Nec Tokin Corp | 非水電解液、ゲル電解質及びそれらを用いた二次電池 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4449907B2 (ja) * | 2003-12-15 | 2010-04-14 | 日本電気株式会社 | 二次電池用電解液およびそれを用いた二次電池 |
CN101033323A (zh) * | 2006-03-09 | 2007-09-12 | Nec东金株式会社 | 聚合物凝胶电解质和使用该电解质的聚合物二次电池 |
-
2009
- 2009-07-09 US US13/382,851 patent/US20120115037A1/en not_active Abandoned
- 2009-07-09 JP JP2011521748A patent/JPWO2011004483A1/ja active Pending
- 2009-07-09 CN CN200980160379XA patent/CN102473966A/zh active Pending
- 2009-07-09 EP EP09847085.9A patent/EP2453511A4/en not_active Withdrawn
- 2009-07-09 WO PCT/JP2009/062531 patent/WO2011004483A1/ja active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1985003075A1 (en) | 1984-01-16 | 1985-07-18 | Cronyn Marshall W | Cancer chemotherapeutic cyclic and acyclic disulfonic ester compounds, method of use therefor, and intermediates |
JP2002100406A (ja) | 2000-09-25 | 2002-04-05 | Toshiba Battery Co Ltd | ポリマーリチウム二次電池及びその製造方法 |
JP2002110245A (ja) * | 2000-10-03 | 2002-04-12 | Maxell Hokuriku Seiki Kk | ポリマー固体電解質リチウムイオン2次電池 |
JP2003257490A (ja) | 2002-02-28 | 2003-09-12 | Mitsubishi Materials Corp | ゲル状ポリマー電解質及びそれを用いたリチウムポリマー電池 |
JP2005310445A (ja) * | 2004-04-19 | 2005-11-04 | Hitachi Maxell Ltd | ゲル状電解質およびそれを用いた電気化学素子 |
JP2007273445A (ja) * | 2006-03-09 | 2007-10-18 | Nec Tokin Corp | ポリマーゲル電解質およびそれを用いたポリマー二次電池 |
JP2009070605A (ja) | 2007-09-11 | 2009-04-02 | Dai Ichi Kogyo Seiyaku Co Ltd | リチウムポリマー電池 |
JP2009140641A (ja) * | 2007-12-04 | 2009-06-25 | Nec Tokin Corp | 非水電解液、ゲル電解質及びそれらを用いた二次電池 |
Non-Patent Citations (2)
Title |
---|
KANEMURA KIYOSHI: "Latest Technology of Polymer Battery II", 2003, CMC PUBLISHING CO., LTD., pages: 242 - 247 |
See also references of EP2453511A4 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8802283B2 (en) * | 2012-01-19 | 2014-08-12 | Samsung Sdi Co., Ltd. | Fabricating method of secondary battery |
US9899703B2 (en) | 2013-03-01 | 2018-02-20 | Nec Corporation | Gel electrolyte and polymer secondary battery using same |
WO2016125726A1 (ja) * | 2015-02-05 | 2016-08-11 | 日立マクセル株式会社 | リチウム二次電池 |
JPWO2016125726A1 (ja) * | 2015-02-05 | 2017-11-16 | マクセルホールディングス株式会社 | リチウム二次電池 |
WO2018150567A1 (ja) * | 2017-02-20 | 2018-08-23 | 日本電気株式会社 | リチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池 |
JPWO2018150567A1 (ja) * | 2017-02-20 | 2019-11-14 | 日本電気株式会社 | リチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池 |
JP7047181B1 (ja) | 2021-12-15 | 2022-04-04 | 第一工業製薬株式会社 | 非水電解液およびリチウムイオン二次電池 |
WO2023112787A1 (ja) | 2021-12-15 | 2023-06-22 | 第一工業製薬株式会社 | 非水電解液およびリチウムイオン二次電池 |
JP2023088767A (ja) * | 2021-12-15 | 2023-06-27 | 第一工業製薬株式会社 | 非水電解液およびリチウムイオン二次電池 |
Also Published As
Publication number | Publication date |
---|---|
CN102473966A (zh) | 2012-05-23 |
EP2453511A4 (en) | 2013-11-27 |
EP2453511A1 (en) | 2012-05-16 |
US20120115037A1 (en) | 2012-05-10 |
JPWO2011004483A1 (ja) | 2012-12-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3982230B2 (ja) | 二次電池用負極およびそれを用いた二次電池 | |
JP5468723B2 (ja) | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 | |
JP5279018B2 (ja) | リチウムイオン二次電池およびその製造方法 | |
WO2011004483A1 (ja) | ポリマーゲル電解質及びそれを用いたポリマー二次電池 | |
JP6123682B2 (ja) | リチウム二次電池 | |
EP1892790A1 (en) | Lithium secondary battery | |
CN111108633B (zh) | 固体电解质电池用正极和包含该正极的固体电解质电池 | |
JP5278994B2 (ja) | リチウム二次電池 | |
JP2007273445A (ja) | ポリマーゲル電解質およびそれを用いたポリマー二次電池 | |
WO2012015033A1 (ja) | リチウムイオン二次電池及びその製造方法 | |
WO2011102453A1 (ja) | ポリマー二次電池およびその製造方法 | |
WO2013042610A1 (ja) | リチウムイオン二次電池 | |
JP5158578B2 (ja) | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 | |
JP6116029B2 (ja) | ゲル電解質およびそれを用いたポリマー二次電池 | |
JP6414058B2 (ja) | 電極用バインダー組成物および電極 | |
KR101110074B1 (ko) | 잉크젯 인쇄용 음극 조성물, 이를 사용하여 제조한 전극 및 리튬 전지 | |
WO2014133169A1 (ja) | 二次電池用電解液およびそれを用いた二次電池 | |
WO2020049843A1 (ja) | 被覆正極活物質、リチウムイオン二次電池の製造方法及びリチウムイオン二次電池 | |
JP2010033830A (ja) | 非水電解質二次電池用負極およびそれを用いた非水電解質二次電池 | |
WO2018150567A1 (ja) | リチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池 | |
JP2007250499A (ja) | リチウムイオン二次電池 | |
JP6319092B2 (ja) | 二次電池 | |
JP2008243718A (ja) | 非水電解液二次電池の製造方法 | |
WO2023112787A1 (ja) | 非水電解液およびリチウムイオン二次電池 | |
WO2014038535A1 (ja) | ポリマーゲル電解質、リチウムイオン電池およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200980160379.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09847085 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011521748 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13382851 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009847085 Country of ref document: EP |