WO2014119554A1 - リチウム電池用電極およびその製造方法、並びにリチウム電池 - Google Patents
リチウム電池用電極およびその製造方法、並びにリチウム電池 Download PDFInfo
- Publication number
- WO2014119554A1 WO2014119554A1 PCT/JP2014/051795 JP2014051795W WO2014119554A1 WO 2014119554 A1 WO2014119554 A1 WO 2014119554A1 JP 2014051795 W JP2014051795 W JP 2014051795W WO 2014119554 A1 WO2014119554 A1 WO 2014119554A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium battery
- electrode plate
- electrode
- positive electrode
- layer
- Prior art date
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 132
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000853 adhesive Substances 0.000 claims abstract description 65
- 230000001070 adhesive effect Effects 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 63
- 230000004913 activation Effects 0.000 claims abstract description 39
- 239000011149 active material Substances 0.000 claims abstract description 33
- 238000009413 insulation Methods 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims description 64
- 239000002002 slurry Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 8
- 150000003949 imides Chemical class 0.000 claims description 7
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 73
- 239000002904 solvent Substances 0.000 abstract description 30
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 49
- 238000001994 activation Methods 0.000 description 34
- 238000001035 drying Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 26
- 229910012572 LiNi0.4Mn0.4Co0.2O2 Inorganic materials 0.000 description 17
- 239000007774 positive electrode material Substances 0.000 description 17
- 238000003825 pressing Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- 239000007773 negative electrode material Substances 0.000 description 14
- -1 nickel metal hydride Chemical class 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 5
- 229910013716 LiNi Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 4
- 229910016118 LiMn1.5Ni0.5O4 Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920006369 KF polymer Polymers 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 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 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007767 slide coating Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 1
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000003341 Bronsted base Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229910004706 CaSi2 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910019974 CrSi Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910005329 FeSi 2 Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012573 LiSiO Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- 229910017028 MnSi Inorganic materials 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910005881 NiSi 2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide 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
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to an electrode for a lithium battery that can be used for a positive electrode plate for a lithium battery, a manufacturing method thereof, and a lithium battery including such an electrode for a lithium battery.
- Lithium batteries can be used repeatedly by charging, and are attracting a great deal of attention in recent years due to the expectation of environmental protection and carbon dioxide reduction.
- lithium batteries have many advantages such as high energy density, light weight, and long life compared to conventional secondary batteries such as nickel metal hydride batteries and lead acid batteries. For this reason, it is widely used as a power source for electronic devices such as mobile phones, notebook personal computers, and electric tools, and has also attracted attention as a power source for driving hybrid vehicles and electric vehicles.
- Patent Document 1 a technique using a maleimide polymer has been reported.
- PVDF polyvinylidene fluoride
- the present invention is intended to solve the problems associated with the prior art as described above, and the positive electrode plate and / or the positive electrode plate and / or the heat activation material dissolved in the organic solvent such as the pyrrolidone solvent is applied to the electrode plate.
- the inventors of the present invention have manufactured a lithium battery electrode (particularly, a positive electrode plate for a lithium battery) manufactured including a specific manufacturing method, and the electrode (particularly, the electrode). It has been found that the above problem can be solved by using a lithium battery obtained by including a positive electrode plate. In addition, the present inventors have also found that the above-mentioned problems can be solved by adopting a specific type of adhesive as an adhesive (or binder) used at a specific site in an electrode for a lithium battery. It was.
- the electrode for a lithium battery of the present invention is An electrode plate, a composite material layer, and a heat insulation layer are provided in this order,
- the composite material layer includes at least a water-based adhesive and an active material,
- the heat insulating layer includes at least a heat activation material, and at least a part of the mixture layer and the heat insulating layer are in contact with each other.
- the heat activation material is preferably a nitrogen-containing polymer that is soluble in an organic solvent and does not swell in water.
- the nitrogen-containing polymer preferably has one or more types selected from the group consisting of amines, amides, imides, maleimides and imines and components derived from dione.
- the aqueous adhesive is preferably one in which at least one of an olefin resin or an acrylic resin is dispersed or dissolved in water.
- the method for producing the electrode for a lithium battery of the present invention comprises: A composite material layer forming step of forming a composite material layer by applying a composite material slurry containing an active material and an aqueous adhesive to the electrode plate surface; A heat insulating layer forming step of forming a heat insulating layer containing a heat activation material on the surface of the composite material layer in this order.
- the heat insulating layer forming step is preferably a step of forming a heat insulating layer by applying a heat activation material dissolved in an organic solvent to the surface of the composite material layer.
- the present invention also provides a lithium battery comprising the above lithium battery electrode.
- the electrode for a lithium battery of the present invention since the swelling of the electrode plate can be reduced, it is possible to provide a lithium battery having both high safety and battery characteristics. Further, according to the production method of the present invention, an electrode having a heat activation material dissolved in an organic solvent such as a pyrrolidone solvent, particularly, a positive electrode plate having a heat activation material dissolved in an organic solvent such as a pyrrolidone solvent is prepared. Even so, the electrode, particularly the positive electrode plate, does not swell. Thereby, a lithium battery having both high safety and battery characteristics can be obtained.
- the lithium battery is suitable as a power source for driving hybrid vehicles and electric vehicles.
- the lithium battery in the present invention includes an electrode for a lithium battery described below.
- the lithium battery generally has a structure including a positive electrode, a negative electrode, a separator, and an electrolytic solution.
- the positive electrode plate (a), the negative electrode plate (b), and the separator (C) includes an electrolyte solution (d) and an exterior material (e), the positive electrode plate and the negative electrode plate are opposed to each other with a separator interposed therebetween, and the entire battery is filled with the electrolyte solution.
- the lithium battery electrode of the present invention described below is used as the positive electrode and / or the negative electrode of the lithium battery, for example, the positive electrode plate (a) and / or the negative electrode plate (b).
- it can be suitably used as a positive electrode, for example, the positive electrode plate (a).
- An exemplary lithium battery according to a particularly preferred embodiment of the present invention includes a positive electrode plate (a) and a negative electrode obtained by including the production method of the present invention (that is, the method for producing a lithium battery electrode of the present invention described later).
- a plate (b), a separator (c), an electrolyte solution (d), and an exterior material (e) are included.
- the positive electrode plate and the negative electrode plate face each other with the separator interposed therebetween, and the entire battery is filled with the electrolyte.
- the lithium battery electrode according to the present invention includes an electrode plate, a composite material layer, and a heat insulating layer in this order.
- the composite material layer includes at least a water-based adhesive and an active material
- the heat insulating layer includes at least a heat activation material. Further, at least a part of the composite material layer and the heat insulating layer are in contact with each other.
- Such a lithium battery electrode of the present invention may be a positive electrode or a negative electrode.
- the lithium battery electrode of the present invention may constitute the positive electrode plate (a) or the negative electrode plate (b) in the above lithium battery.
- the lithium battery electrode of the present invention is used as a positive electrode.
- the lithium battery electrode of the present invention constitutes the positive electrode plate (a).
- the positive electrode plate (a) is a step of preparing a mixture slurry (also referred to as an electrode slurry) containing at least a positive electrode active material and an aqueous adhesive, and then applying the slurry to the electrode plate surface to form an electrode mixture layer; It can be obtained by including a step of forming a heat insulating layer containing a heat activation material on the surface of the electrode mixture layer.
- a mixture slurry also referred to as an electrode slurry
- the positive electrode plate (a) is a step of preparing a mixture slurry (also referred to as an electrode slurry) containing at least a positive electrode active material and an aqueous adhesive, and then applying the slurry to the electrode plate surface to form an electrode mixture layer; It can be obtained by including a step of forming a heat insulating layer containing a heat activation material on the surface of the electrode mixture layer.
- the composite material layer constituting the lithium battery electrode of the present invention includes at least a water-based adhesive and an active material.
- the composite material layer used in the present invention contains an active material, it functions as a place where an electrode reaction occurs.
- the electrode for a lithium battery of the present invention can be used for either a positive electrode or a negative electrode. That is, when the active material constituting the composite material layer is a positive electrode active material described later, the lithium battery electrode of the present invention functions as a positive electrode and can be used as the positive electrode plate (a). On the other hand, when the active material constituting the composite layer is a negative electrode active material described later, the lithium battery electrode of the present invention functions as a negative electrode and can be used as a negative electrode plate (b).
- the lithium battery electrode of the present invention is a lithium battery electrode in which the active material constituting the composite layer is a positive electrode active material, and in this case functions as a positive electrode. Used as a positive electrode plate (a).
- the composite material layer may also be referred to as an “electrode composite material layer”.
- the positive electrode active material that can form the composite layer a known material used for electrochemical cells can be used.
- the negative electrode active material is not particularly limited as long as it can be doped / undoped with lithium ions, and known materials can be used.
- a carbide, a lithium alloy, and a metal oxide can be given.
- the carbide includes carbon powder, graphite, carbon fiber, and carbon nanotube.
- the lithium alloy include lithium and silicon atoms, tin atoms, germanium atoms alone or oxides, carbides, nitrides, carbonitrides and the like containing them.
- the negative electrode active material containing silicon atoms includes silicon alloys, boron, nitrogen, oxygen or carbon and silicon compounds, tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium. , Bismuth, antimony or chromium.
- silicon alloys or compounds include SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2 , MnSi.
- the negative electrode active material containing tin atoms include silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium, or alloyed tin, oxygen, Examples thereof include compounds of carbon or nitrogen and tin.
- Examples of the negative electrode active material containing germanium atoms include silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony or chromium-containing or alloyed germanium, oxygen, Examples include compounds of carbon or nitrogen and germanium.
- LiAl, Li 3 Cd, Li 4.4 Pb, In 2 O, In 2 O 3 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Ag 2 O, AgO, Ag 2 O 3 , ZnO, CoO, NiO, FeO, TiO 2 , Li 3 Ti 5 O 12 can be mentioned.
- These negative electrode active materials may be used individually by 1 type, and may be used in combination of 2 or more.
- active material may be used as a concept encompassing the positive electrode active material and the negative electrode active material.
- the water-based adhesive examples include an adhesive using water as a solvent and an emulsion adhesive using water as a dispersion medium.
- the water-based adhesive is used as a binder for disposing the active material on the surface of the electrode plate (current collector).
- the water-based adhesive includes a water-based adhesive.
- the water-based adhesive is one in which the adhesive component is dissolved in water or the adhesive component particles are dispersed in water.
- dispersed refers to a state in which particles are dispersed in the adhesive without visual aggregation, and some of the particles may be dissolved.
- the adhesive component include polymers such as olefin resins and acrylic resins.
- the polymer contained in the water-based adhesive is not particularly limited as long as it functions as an adhesive component, can be dissolved or dispersed in water, and does not impair the function of the composite material layer. It is a polymer composed of one or more monomers of each of a monomer, a diene, a halogen, a vinyl, a silicone, a halogenated olefin, a urethane, an amide, and an imide. Olefin-based, acrylic-based and diene-based are preferable.
- Examples of the olefin monomer that can constitute such a polymer include ethylene, propylene, and 1-butene.
- Examples of acrylic monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid iso-butyl, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, acrylonitrile, methacrylonitrile, Examples include acrylamide, methacrylamide, and acrylic sulfonic acid.
- Examples of the diene monomer include butadiene.
- Examples of the silicone monomer include diorganosiloxane or organosiloxane having a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, or the like.
- Examples of the halogen monomer include tetrafluoroethylene and chlorotrifluoroethylene.
- Examples of the vinyl monomer include vinyl alcohol, vinyl acetate, divinylbenzene, styrene, and vinyl stearate.
- the water-based adhesive is preferably a polyolefin-based adhesive having at least one olefin monomer as a constituent unit.
- the method for synthesizing the water-based adhesive dispersed or dissolved in water is not particularly limited as long as the polymer is dispersed or dissolved in water, and the production method thereof is not particularly limited.
- a method of synthesizing and dispersing or dissolving in water a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or a solution polymerization method can be employed.
- a method in which a polymer is prepared in advance and the molten resin is forcibly torn off by stirring in water, and a method in which water is added to the melt-kneaded resin by an extruder can be employed.
- the water-based adhesive of the present invention may be mixed with other solvent in water as long as the effects of the present invention are exhibited.
- Solvents to be mixed with water include aliphatic alcohols such as ethanol and isopropyl alcohol, ketone solvents such as acetone, methyl isobutyl ketone and methyl ethyl ketone, ester solvents such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone, Examples thereof include amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide. When mixing, you may use individually by 1 type or in mixture of 2 or more types.
- the amount ratio of the positive electrode active material and the water-based adhesive when preparing the mixture slurry is not particularly limited, but the water-based material with respect to 100 parts by mass of the positive electrode active material.
- the adhesive is preferably 1 to 20 parts by mass (in terms of solid content).
- the amount ratio of the negative electrode active material and the aqueous adhesive when preparing the mixture slurry is not particularly limited, but is 100 parts by mass of the negative electrode active material.
- the aqueous adhesive is preferably 0.5 to 20 parts by mass (in terms of solid content).
- an appropriate component used for producing the composite material layer may be contained.
- the composite material layer used in the present invention when the composite material layer used in the present invention is formed from a composite material slurry, the composite material layer may contain various compounding components derived from the composite material slurry.
- various compounding components derived from such a composite slurry include known thickening agents, known conductive aids such as (conductive) carbon black and graphite, and surfactants, dispersants, wetting agents, antifoaming agents. And other additives. Specific examples of these various blending components are described in the section “Method for forming a composite material layer” described below.
- the composite material layer constituting the electrode for a lithium battery according to the present invention is prepared on the surface of the current collector (electrode plate) after creating an aqueous composite slurry (also referred to as “composite slurry” in this specification).
- the slurry can be applied and dried.
- the active material and the water-based adhesive are included as essential components in the synthetic slurry.
- the step of forming the mixture layer by applying the mixture slurry to the surface of the electrode plate in this manner is called a mixture layer forming step. is there.
- the mixture slurry may contain a thickener in addition to the active material and the water-based adhesive which are essential components.
- a thickener known ones used for electrochemical cells can be used.
- cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof (modified) ) Poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; (Modified) Polyvinyl alcohol, acrylic acid or copolymers of acrylate and vinyl alcohol, maleic anhydride or maleic acid or fumaric acid and vinyl alcohol
- Polyvinyl alcohols such as copolymers with polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified polyacrylic acid, oxidized starch, phosphate starch, casein, various modified starches, etc. That.
- the mixture slurry may contain a known conductive aid such as (conductive) carbon black and graphite.
- an additive can be added to the mixture slurry.
- the additive is not particularly limited as long as the effects of the present invention are exhibited.
- surfactants there are surfactants, dispersants, wetting agents, antifoaming agents and the like.
- the type of the stirrer is not limited. Examples include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a planetary mixer, a Hobart mixer, and a high-speed stirrer.
- the application and drying method is not particularly limited.
- methods such as slot die coating, slide coating, curtain coating, or gravure coating may be used.
- the drying method include drying with warm air, hot air, low-humidity air, vacuum drying, and (far) infrared rays.
- the drying time and drying temperature are not particularly limited, but the drying time is usually 1 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
- the method may include a step of lowering the porosity of the active material layer by pressure treatment using a die press or a roll press after applying and drying the mixture slurry on the current collector. preferable.
- the heat insulating layer includes at least a heat activation material.
- the lithium battery electrode of the present invention at least a part of the composite material layer and the heat insulating layer are in contact with each other.
- the heat insulating layer is present in a form in which at least a part thereof is in contact with at least a part of the composite material layer.
- a heat insulating layer containing a heat activation material is formed on the surface of the electrode mixture layer (that is, the mixture layer).
- the heat activation material constituting the heat insulation layer in the present invention is a material that is activated and causes a cross-linking reaction when the temperature of the lithium battery rises. Then, the heat-activated material is converted into a polymer, so that lithium ions are prevented from diffusing and the conductivity of the electrolytic solution is lowered. In addition, by suppressing the release of oxygen molecules from the positive electrode through such a crosslinking reaction, the exothermic reaction between the positive electrode and the electrolyte is suppressed, and the safety of the lithium battery is also improved.
- Thermal activation material As the heat activation material, there is no particular limitation on the material of the heat activation material as long as it exhibits such a function and can maintain the function of the present invention, but nitrogen that is soluble in an organic solvent and does not swell in water. It is preferable that it is a containing polymer.
- the “organic solvent” is preferably an organic solvent having a solubility parameter (SP value) of 22 to 26 (MPa) 1/2 .
- SP value solubility parameter
- the SP value of the solvent can be determined by the method described in, for example, “Polymer Handbook”, 4th edition, pages VII-675 to VII-711. Specifically, Table 1 (VII- 683) and Tables 7 to 8 (VII-688 to VII-711). Further, the SP value in a mixed solvent of a plurality of solvents can be determined by a known method. For example, the SP value of the mixed solvent can be obtained as the sum of products of the SP value of each solvent and the volume fraction, assuming that additivity is established.
- “does not swell in water” means that the swelling ratio obtained by the following method is 100% or less.
- heat activation material for example, heat activation materials described in JP 2012-134149 A and JP 2012-138359 A can be used. That is, suitable nitrogen-containing polymers that can be used in the present invention include nitrogen-containing compounds having a number average molecular weight of at least 1500, or nitrogen-containing oligomers having a number average molecular weight of about 200-2999.
- the heat-activated material comprises a nitrogen-containing polymer
- the nitrogen-containing polymer is a group consisting of an amine, an amide, an imide, a maleimide, and an imine. It may be a hyper branched polymer formed by reaction of one or more selected from dione with dione. That is, in a preferred embodiment of the present invention, the nitrogen-containing polymer has at least one selected from the group consisting of amines, amides, imides, maleimides and imines, and a component derived from dione.
- specific examples of amine, amide, imide, maleimide and imine constituting the nitrogen-containing polymer include those described in JP 2012-134149 A.
- diones include barbituric acid, derivatives of barbituric acid, acetylacetone, or derivatives of acetylacetone.
- a nitrogen-containing polymer obtained by containing a bismaleimide monomer such as N, N′-bismaleimide-4,4′-diphenylmethane (BMI) and barbituric acid (BTA) is preferable.
- the molar ratio of the required amount of dione and the amine, amide, imide, maleimide or imine monomer is about 1:20 to 4: 1. More preferably, the molar ratio is about 1: 5 to 2: 1. More preferably, the molar ratio is about 1: 3 to 1: 1.
- the heat activation material is usually uniformly dispersed in the heat insulating layer before the heat activation.
- the heat activation material is a micromolecular material before heat activation. Therefore, the diffusion of lithium ions in the lithium battery is not affected by the thermally activated material.
- a crosslinking reaction occurs in the thermally activated material, and the thermally activated material is converted into a polymer. Therefore, the diffusion of lithium ions is delayed, and the conductivity of the electrolytic solution is lowered, so that safety can be improved.
- the end groups of the thermally activated material cause a cross-linking reaction to prevent lithium ion diffusion.
- the temperature of the crosslinking reaction of the thermally activated material is the onset temperature.
- the end groups of the heat activated material include ethenyl groups (from bismaleimide) and amino groups (from barbituric acid).
- the heat activation temperature is about 80 to 280 ° C. More preferably, the thermal activation temperature is about 100-220 ° C. More preferably, the thermal activation temperature is about 130-200 ° C.
- the heat insulating layer may be Al, Mg, Si, Zr, Ti, Zn, Li, Co, or an oxide thereof, a hydroxide thereof, a sulfide thereof, or the like depending on the purpose.
- Inorganic materials such as nitrides, their halides, and also lithium-containing salts such as Li 2 CO 3 , or lithium-containing oxides, hydroxides, sulfides, nitrides, carbonates, halides May be.
- a Bronsted basic solvent such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAC), pyrrolidone, N-dodecylpyrrolidone, or Bronsted such as ⁇ -butyrolactone (GBL).
- NMP N-methylpyrrolidone
- DMF dimethylformamide
- DMAC dimethylacetamide
- pyrrolidone N-dodecylpyrrolidone
- GBL ⁇ -butyrolactone
- An adhesive such as polyvinylidene fluoride dissolved or dispersed in a neutral solvent or a solvent obtained by combining these solvents may be included.
- the method for forming the heat insulating layer on the surface of the electrode mixture layer is not particularly limited, but a method by coating is preferable.
- the heat insulating layer can be formed by applying a heat activation material dissolved in an organic solvent to the surface of the mixture layer. In this case, the organic solvent contained in the applied slurry is then evaporated, and the application of the heat activation material and other optional components is established, and at least the heat insulation layer containing the heat activation material Is formed on the surface of the composite material layer.
- the coating method is preferably slot / die coating, slide coating, curtain coating, or gravure coating.
- a spray coating method can also be used.
- the coating liquid is usually a liquid containing a heat activation material and a suitable organic solvent.
- suitable organic solvents constituting such a coating liquid include N-methylpyrrolidone (NMP), dimethylformamide.
- NMP N-methylpyrrolidone
- DMAC dimethylacetamide
- pyrrolidone N-dodecylpyrrolidone
- GBL ⁇ -butyrolactone
- the process of forming the heat insulation layer containing a heat activation material in the surface of the said composite material layer may be called a heat insulation layer formation process.
- the thickness of the heat insulating layer is not particularly limited, but is preferably about 0.1 to 50 ⁇ m.
- the manufacturing method of the electrode for a lithium battery according to the present invention is as follows: A composite material layer forming step of forming a composite material layer by applying a composite material slurry containing an active material and an aqueous adhesive to the electrode plate surface; A heat insulating layer forming step of forming a heat insulating layer containing a heat activation material on the surface of the composite material layer in this order.
- Such a manufacturing method of the present invention provides a lithium battery electrode including an electrode plate, a composite material layer, and a heat insulating layer in this order.
- the formed mixture layer includes at least an aqueous adhesive and an active material
- the formed heat insulating layer includes at least a heat activation material.
- positive electrode active materials and negative electrode active materials used as active materials in the composite material layer forming step those described above in the “positive electrode active material” and “negative electrode active material” sections in the above “composite material layer” can be used respectively.
- an aqueous adhesive and “other component” in the said “mixture layer” can be used as an aqueous adhesive and the other various compounding components which can comprise a synthetic
- heat activation material and other components that can constitute the heat insulation layer those described above as the “heat activation material” and “other components” in the “heat insulation layer”, respectively. Can be used.
- the specific operation performed in the composite material layer forming step is as described above in the section “Method of forming the composite material layer” in the above “composite material layer”, and the specific operation performed in the heat insulating layer forming step.
- the operation is as described above in the section “Method for forming a heat insulating layer” in the above “heat insulating layer”.
- Lithium battery In the present invention, a lithium battery is also provided as a third invention.
- the lithium battery according to the present invention includes the above-described lithium battery electrode.
- the lithium battery generally has a structure including a positive electrode, a negative electrode, a separator, and an electrolyte solution.
- the positive electrode plate and the negative electrode plate are opposed to each other with the separator interposed therebetween, and the whole battery is filled with the electrolytic solution.
- the lithium battery of the present invention includes the above-described lithium battery electrode in the form of a positive electrode and / or a negative electrode, for example, the positive electrode plate (a) and / or the negative electrode plate (b).
- the positive electrode for example, the positive electrode plate (a) is an electrode employing a positive electrode active material as an active material among the electrodes for a lithium battery of the present invention, or the production of the present invention.
- This is an electrode for a lithium battery obtained by the method and employing a positive electrode active material as an active material.
- the above-described lithium battery electrode according to the present invention is suitably used as the positive electrode, for example, the positive electrode plate (a).
- the lithium battery according to the present invention employs a positive electrode active material as an active material and includes the above-described lithium battery electrode that functions as the positive electrode, for example, the positive electrode plate (a).
- Such a positive electrode for example, the above-described lithium battery electrode that functions as the positive electrode plate (a) can be suitably obtained by using the positive electrode active material as an active material by the above-described method for producing a lithium battery electrode. That is, in a preferred embodiment of the present invention, after preparing a positive electrode, for example, the positive electrode plate (a), a mixed material slurry (also referred to as an electrode slurry) containing at least a positive electrode active material and an aqueous adhesive, It can be obtained by including a step of forming an electrode mixture layer by coating on the surface of the plate and a step of forming a heat insulating layer containing a heat activation material on the surface of the electrode mixture layer.
- a mixed material slurry also referred to as an electrode slurry
- a negative electrode (or a negative electrode plate) having a conventionally known configuration can be used as the negative electrode, for example, the negative electrode plate (b), and the above-described lithium battery electrode according to the present invention is used. It can also be used.
- the negative electrode for example, the negative electrode plate (b)
- the negative electrode for example, the negative electrode plate (b)
- the negative electrode active material can be used as the active material.
- the negative electrode for example, the negative electrode plate (b) may have a conventionally known configuration.
- the negative electrode, for example, the negative electrode plate (b) is prepared by, for example, preparing a mixed material slurry containing a negative electrode active material, applying the slurry to the surface of the current collector (electrode plate), and drying the mixture slurry.
- the method for producing the electrode composite layer (composite layer) can be referred to.
- non-aqueous solvents such as a polyvinylidene fluoride
- non-aqueous solvents such as a polyvinylidene fluoride
- the mixture slurry may contain a conductive additive such as (conductive) carbon black.
- a separator (c) is disposed between the positive electrode plate and the negative electrode plate.
- materials (fine) porous polyethylene, (fine) porous polypropylene, Teflon (registered trademark) film, polyamide film, polyvinyl chloride film, polyvinylidene fluoride film, polyaniline film, polyimide film, non-woven fabric, polyethylene terephthalate,
- Teflon (registered trademark) film polyamide film, polyvinyl chloride film, polyvinylidene fluoride film, polyaniline film, polyimide film, non-woven fabric, polyethylene terephthalate
- a multilayer composite structure in which two or more of polystyrene cellulose or these polymers are combined.
- other resin excellent in thermal stability may be coated.
- a porous heat-resistant layer containing a heat-resistant filler and an adhesive may exist between the negative electrode plate and the separator.
- the heat resistant filler inorganic oxides such as alumina, silica, titania, zirconia, magnesia, yttria, ceramics, glass, and the like can be used. These may be used alone or in combination of two or more.
- a non-aqueous solvent containing a non-aqueous binder such as polyvinylidene fluoride can be used in addition to the aqueous solvent containing the aqueous adhesive described in the method for producing the electrode mixture layer.
- the heat-resistant filler is preferably 0.5 to 20 parts by mass (converted to solid content) with respect to 100 parts by mass.
- the electrolyte solution (d) is immersed in the entire positive electrode plate, negative electrode plate, and separator.
- the electrolyte include propylene carbonate, ethylene carbonate, ⁇ -butyrolactone, dimethyl sulfoxide, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, and the like. Are used alone or in admixture of two or more. Lithium salt is dissolved in the electrolyte.
- Lithium salts include organic solvents such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , CF 3 SO 3 Li, (CF 3 SO 2 ) 2 N ⁇ Li, etc., alone or in combination of two or more. Those dissolved in can be used. If necessary, additives such as vinylene carbonate, 1,3-propene sultone, lithium bis (oxalate) borate (LiBOB), and a maleimide compound may be added to the electrolytic solution.
- organic solvents such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , CF 3 SO 3 Li, (CF 3 SO 2 ) 2 N ⁇ Li, etc.
- additives such as vinylene carbonate, 1,3-propene sultone, lithium bis (oxalate) borate (LiBOB), and a maleimide compound may be added to the electrolytic solution.
- a metal can, for example, a can made of iron, stainless steel, aluminum or the like is preferable. Moreover, you may use the film-form bag which laminated the ultra-thin aluminum with resin.
- the shape of the exterior material may be any of a cylindrical shape, a square shape, a thin shape, a coin shape, and the like.
- Example 1 ⁇ Production of Lithium Battery Aqueous Positive Plate LiNi 0.4 Mn 0.4 Co 0.2 O 2 > (Preparation of mixture slurry) LiNi 0.4 Mn 0.4 Co 0.2 O 2 100 parts by weight, conductive carbon black (Timcal SuperP) 4.44 parts by weight, graphite (Timcal KS-6) 2.22 parts by weight, carboxy previously dissolved in water Methylcellulose (Daiichi Kogyo Seiyaku Co., Ltd. WS-A) 1.11 parts by weight in terms of solid content, and olefin-based aqueous adhesive (Mitsui Chemicals, Inc.
- Chemipearl EVS6500N dispersed in water in terms of solid content 4.44 weight part was added and the mixture slurry was created using the planetary mixer and the high-speed stirrer (made by Inoue Seisakusho). Further, water was added for viscosity adjustment to adjust dispersion.
- the mixture slurry obtained above was applied to the current collector for the positive electrode plate and dried.
- a coating machine manufactured by Inoue Metal Industry Co., Ltd.
- the conditions of the aqueous slurry in each of the three zones were 60, 90, and 120 ° C. in the first, second, and third drying zones, respectively.
- the wind speed was set to 12 m / s.
- the mixture slurry was applied and dried on one surface of an aluminum foil having a thickness of 20 ⁇ m, which was a current collector for a positive electrode plate. Similarly, the other surface was coated and dried to obtain a precursor electrode for a positive electrode plate.
- the coating amount per side was 12 mg / cm 2 after drying.
- the prepared electrode that is, the positive electrode precursor electrode
- the treatment was performed so that the density of the electrode mixture layer was 3 g / cm 3 .
- N, N'-bismaleimide-4,4'-diphenylmethane (manufactured by Hakuei) and barbituric acid (manufactured by Hakuei) were added at a ratio of 2: 1 to a 1 L flask containing N-methylpyrrolidone. The mixture was stirred for 48 hours at ° C.
- the resulting solution was diluted to a 2% solution.
- the coating solution for the heat-insulating layer was applied onto the electrode that was finished up to the pressing step (that is, the rolling precursor electrode for the positive electrode plate) and dried. Drying conditions were 100, 130, and 150 ° C. The wind speed was set to 12 m / s. Coating was performed so that the film thickness at the time of coating was 12.5 ⁇ m. As a result, a positive electrode plate was obtained.
- Example 2 Using the obtained mixture slurry, it was applied to the current collector for the positive electrode plate in the same manner as in Example 1. In addition, the conditions of the slurry of each drying zone which has three zones were performed at 100, 110, and 120 degreeC higher temperature than an aqueous slurry. The coating amount per side was 12 mg / cm 2 after drying.
- Example 2 Using the obtained precursor electrode for a positive electrode plate, a pressing step and a heat insulating layer were applied in the same manner as in Example 1 to obtain a positive electrode plate.
- Example 1 the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 1-1, and in Comparative Example 1, the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 1-2.
- Example 2 ⁇ Preparation of LiMn 2 O 4 water-based positive electrode plate for lithium batteries> A mixture slurry was prepared in the same manner as in Example 1. Only the active material was changed from LiNi 0.4 Mn 0.4 Co 0.2 O 2 to LiMn 2 O 4 . The coating was also performed in the same manner as in Example 1. The coating amount per side was 20 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 2.5 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 2 the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 2-1, and in Comparative Example 2, the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 2-2.
- Example 3 ⁇ Preparation of LiPoO 2 aqueous positive electrode plate for lithium batteries> A mixture slurry was prepared in the same manner as in Example 1. Only the active material was changed from LiNi 0.4 Mn 0.4 Co 0.2 O 2 to LiCoO 2 . The coating was also performed in the same manner as in Example 1. The coating amount per side was 15 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 3 the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 3-1, and in Comparative Example 3, the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 3-2.
- Example 4 ⁇ Manufacture of LiMn 1.5 Ni 0.5 O 4 water based positive electrode plate for lithium batteries> A mixture slurry was prepared in the same manner as in Example 1. Only the active material was changed from LiNi 0.4 Mn 0.4 Co 0.2 O 2 to LiMn 1.5 Ni 0.5 O 4 . The coating was also performed in the same manner as in Example 1. The coating amount per side was 15 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 2.5 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 4 the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 4-1, and in Comparative Example 4, the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 4-2.
- Example 5 ⁇ Preparation of LiFePO 4 water-based positive electrode plate for lithium batteries> A mixture slurry was prepared in the same manner as in Example 1. Only the active material was changed from LiNi 0.4 Mn 0.4 Co 0.2 O 2 to LiFePO 4 . The coating was also performed in the same manner as in Example 1. The coating amount per side was 16 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 2 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 5 the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 5-1, and in Comparative Example 5, the positive electrode plate not coated with the heat insulating layer was referred to as Reference Example 5-2.
- Example 6 ⁇ Preparation of LiNi battery aqueous positive electrode LiNi 0.4 Mn 0.4 Co 0.2 O 2 -polypropylene adhesive> A mixture slurry was prepared in the same manner as in Example 1. Only the adhesive was changed from an olefin-based aqueous adhesive (Mitsui Chemicals, Chemipearl EVS6500N) to a polypropylene-based adhesive. The coating was also performed in the same manner as in Example 1. The coating amount per side was 12 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- an olefin-based aqueous adhesive Mitsubishi Chemicals, Chemipearl EVS6500N
- Example 7 ⁇ Preparation of LiNi 0.4 Mn 0.4 Co 0.2 O 2 -SBR Adhesive Aqueous Plate for Lithium Battery>
- a mixture slurry was prepared in the same manner as in Example 1. Only the adhesive was changed from an olefin-based aqueous adhesive (Mitsui Chemicals, Chemipearl EVS6500N) to SBR (styrene-butadiene latex).
- the coating was also performed in the same manner as in Example 1.
- the coating amount per side was 12 mg / cm 2 after drying.
- the pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 .
- the heat insulating layer was also applied in the same manner as in Example 1.
- Example 8 ⁇ Preparation of LiNi 0.4 Mn 0.4 Co 0.2 O 2 -Acrylic Adhesive Aqueous Plate for Lithium Batteries> A mixture slurry was prepared in the same manner as in Example 1. Only the adhesive was changed from an olefin-based aqueous adhesive (Mitsui Chemicals, Inc., Chemipearl EVS6500N) to an acrylic adhesive (styrene-methacrylic acid). The coating was also performed in the same manner as in Example 1. The coating amount per side was 12 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- an olefin-based aqueous adhesive Mitsubishi Chemicals, Inc., Chemipearl EVS6500N
- acrylic adhesive styrene-methacrylic acid
- Example 9 ⁇ Preparation of Lithium Battery Aqueous Cathode Plate LiNi 0.4 Mn 0.4 Co 0.2 O 2 -Thickener Polyvinyl Alcohol> A mixture slurry was prepared in the same manner as in Example 1. The thickener was changed from carboxymethyl cellulose to polyvinyl alcohol (KL-318 manufactured by Kuraray Co., Ltd.). The coating was also performed in the same manner as in Example 1. The coating amount per side was 12 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 10 ⁇ Production of LiNi battery water / organic solvent mixed cathode plate LiNi 0.4 Mn 0.4 Co 0.2 O 2 > A mixture slurry was prepared in the same manner as in Example 1. Isopropyl alcohol was added 10% to the solvent water. Coating was performed in the same manner as in Example 1. The coating amount per side was 12 mg / cm 2 after drying. The pressing step was performed so that the density of the electrode mixture layer was 3 g / cm 3 . The heat insulating layer was also applied in the same manner as in Example 1.
- Example 11 ⁇ Creation of Al 2 O 3 containing heat insulating layer> 100% by weight of Al 2 O 3 , PVDF dissolved in N-methylpyrrolidone (KF Polymer W1300, Kureha Chemical Co., Ltd.) 4.44 parts by weight in terms of solid content, N, N ′ dissolved in N-methylpyrrolidone A solution synthesized from -bismaleimide-4,4'-diphenylmethane and barbituric acid was added, and a slurry was prepared using a planetary mixer and a high-speed stirrer (manufactured by Inoue Seisakusho). Further, N-methylpyrrolidone was added for viscosity adjustment to adjust dispersion. The solution was applied to the positive electrode plate of Reference Example 1-1.
- Example 11 A slurry prepared in the same manner as in Example 11 was applied to the positive electrode plate of Reference Example 1-2.
- Example 12 ⁇ Creation of thermal insulation layer containing Li 2 CO 3 > 100% by weight of Li 2 CO 3 , PVDF dissolved in N-methylpyrrolidone (KF Polymer W1300, Kureha Chemical Co., Ltd.) 4.44 parts by weight in terms of solid content, N, N ′ dissolved in N-methylpyrrolidone A solution synthesized from -bismaleimide-4,4'-diphenylmethane and barbituric acid was added, and a slurry was prepared using a planetary mixer and a high-speed stirrer (manufactured by Inoue Seisakusho). Further, N-methylpyrrolidone was added for viscosity adjustment to adjust dispersion. The solution was applied to the positive electrode plate of Reference Example 1-1.
- Example 12 A slurry prepared in the same manner as in Example 12 was applied to the positive electrode plate of Reference Example 1-2.
- Electrode adhesion evaluation> Using the obtained positive electrode plate, the electrode plate after the heat insulation layer coating was cut out to a size of 1.5 cm ⁇ 2 cm, attached to a glass preparation with an instantaneous adhesive, and the electrode was fixed to obtain a sample for evaluation.
- the sample for evaluation is cut between the electrode mixture layer and the positive electrode plate at a horizontal speed of 2 ⁇ m / second by a coating film peel strength measuring device Cycus DN20 type (manufactured by Daipla Intes Co., Ltd.), and the horizontal force necessary for the cutting is cut.
- the peel strength (kN / m) of the electrode mixture layer was measured. Based on the obtained results, standardization was performed according to “Example / corresponding reference example”. The results are shown in Table 1. The larger the value, the stronger the adhesive strength.
- the mixture slurry was applied to the current collector for the negative electrode plate and dried by the coating machine used for the positive electrode plate.
- the conditions for each of the three zones were 100, 110, and 120 ° C.
- the wind speed was set to 12 m / s.
- Both sides were coated and dried on a copper foil having a thickness of 10 ⁇ m, which was a current collector for the negative electrode plate, to obtain a precursor electrode for the negative electrode plate.
- the coating amount per side was set to 11.3 mg / cm 2 after drying.
- the prepared electrode (that is, the negative electrode precursor electrode) was rolled with a roll press to obtain a negative electrode plate. Processing was performed so that the density of the electrode mixture layer was 1.5 g / cm 3 .
- non-aqueous electrolyte for lithium battery
- EC ethylene carbonate
- MEC methyl ethyl carbonate
- a non-aqueous electrolyte was prepared so that the concentration was 1.0 mol / liter.
- the battery positive electrode can is covered with a polypropylene gasket and the can lid is caulked to maintain the airtightness of the battery, and a coin-type lithium battery having a diameter of 20 mm and a height of 3.2 mm is produced. did.
- the battery was discharged to a predetermined voltage with a constant current value of 0.1C.
- the discharge capacity at this time was defined as the initial discharge capacity (mAh / g).
- the fully charged coin-type lithium battery was fully charged. Thereafter, the battery was disassembled, and the fully charged positive electrode plate was set in a differential scanning calorimeter, and measurement was performed. The heating rate was 10 ° C./min. Safety performance was evaluated from the calorific value of the obtained decomposition peak and the temperature reached. The obtained results are shown in Table 3. A lower calorific value and a higher peak shift indicate higher safety performance.
Abstract
Description
極板と、合材層と、断熱層とをこの順で備え、
前記合材層は少なくとも水系接着剤と活物質とを含み、
前記断熱層は少なくとも熱活性化材料を含み、かつ
前記合材層および前記断熱層の少なくとも一部が接触している。
活物質と水系接着剤とを含む合材スラリーを極板表面に塗布して合材層を形成する合材層形成工程と、
前記合材層の表面に熱活性化材料を含む断熱層を形成する断熱層形成工程と
をこの順で含む。
本発明に係るリチウム電池用電極は、極板と、合材層と、断熱層とをこの順で備える。
正極板(a)は、少なくとも正極活物質と水系接着剤を含む合材スラリー(電極スラリーとも称す)を調製後、該スラリーを極板表面に塗布して電極合材層を形成する工程と、該電極合材層の表面に熱活性化材料を含む断熱層を形成する工程を含むことで得られる。
本発明のリチウム電池用電極を構成する合材層は、少なくとも水系接着剤と活物質とを含む。ここで、本発明で用いられる合材層は、活物質を含むことから、電極反応が起こる場として機能する。
本発明において、合材層を構成しうる正極活物質は、電気化学セル用として用いられる公知のものを使用することができる。ここで、本発明において使用することができる正極活物質として、例えばLiMnO2、LiMn2O4、LiCoO2、Li2Cr2O7、Li2CrO4、LiNiO2、LiFeO2、LiNixCo1-xO2 (0<x<l)、LiMPO4 (M=Feなどの遷移金属)、LiMn0.5Ni0.5O2、LiNixCoyMnzO2 (x+y+z=l)、LiNixCoyAlzO2 (x+y+z=l)、LiM0.5Mn1.5O4(M=II価金属)のなどのリチウムと遷移金属とからなる複合酸化物及び、ポリアニリン、ポリチオフェン、ポリピロール、ポリアセチレン、ポリアセン、ジメルカプトチアジアゾール/ポリアニリン複合体などの有機高分子材料などが挙げられる。
負極活物質としては、リチウムイオンをドープ・脱ドープできるものであれば特に制限はなく公知のものを使用できる。例えば、炭化物、リチウム合金、金属酸化物が挙げられる。炭化物は、炭素粉末、グラファイト(graphite)、炭素繊維、カーボンナノチューブがある。リチウム合金は、リチウムと、ケイ素原子、スズ原子、ゲルマニウム原子単独もしくはそれらを含む酸化物、炭化物、窒化物、炭窒化物等が挙げられる。また、ケイ素原子を含む負極活物質としては、ケイ素の合金、ホウ素、窒素、酸素または炭素とケイ素との化合物、スズ、ニッケル、銅、鉄、コバルト、マンガン、亜鉛、インジウム、銀、チタン、ゲルマニウム、ビスマス、アンチモンまたはクロムを含むものが挙げられる。ケイ素の合金あるいは化合物の一例としては、SiB4、SiB6、Mg2Si、Ni2Si、TiSi2、MoSi2、CoSi2、NiSi2、CaSi2、CrSi2、Cu5Si、FeSi2、MnSi2、NbSi2、TaSi2、VSi2、WSi2、ZnSi2、SiC、Si3N4、Si2N2O、SiOx(0<x≦2)あるいはLiSiOなどが挙げられる。スズ原子を含む負極活物質としては、例えば、ケイ素、ニッケル、銅、鉄、コバルト、マンガン、亜鉛、インジウム、銀、チタン、ゲルマニウム、ビスマス、アンチモンまたはクロムを含むまたは合金化したスズや、酸素、炭素または窒素とスズとの化合物が挙げられる。ゲルマニウム原子を含む負極活物質としては、例えば、ケイ素、ニッケル、銅、鉄、コバルト、マンガン、亜鉛、インジウム、銀、チタン、ゲルマニウム、ビスマス、アンチモンまたはクロムを含むまたは合金化したゲルマニウムや、酸素、炭素または窒素とゲルマニウムとの化合物が挙げられる。それ以外にも、LiAl、Li3Cd、Li4.4Pb、In2O、In2O3、PbO、PbO2、Pb2O3、Pb3O4、Ag2O、AgO、Ag2O3、ZnO、CoO、NiO、FeO、TiO2、Li3Ti5O12が挙げられる。これら負極活物質は1種単独で用いてもいいし、2つ以上を組み合わせて用いてもよい。
水系接着剤は、水を溶媒とする接着剤および水を分散媒とするエマルジョン接着剤などである。本発明においては、水系接着剤は、上記極板(集電体)の表面に上記活物質を配置するためのバインダーとして用いられるところ、本発明のリチウム電池用電極において、水系接着剤を含む合材層を採用することで、ピロリドン系溶媒などの有機溶媒を用いて後述する断熱層を形成しても、得られる電極が、正極板および/または負極板として用いられたときに膨潤しない効果を有する。このような効果は、正極、例えば、正極板(a)に、水系接着剤を含む合材層を有する本発明のリチウム電池用電極を適用したときに、特に有利に得られる。
本発明で用いられる合材層には、上記活物質および水系接着剤に加えて、合材層を製造するために用いられる適当な成分が含まれていてもよい。例えば、本発明で用いられる合材層が合材スラリーから形成される場合、合材層には、その合材スラリー由来の各種配合成分が含まれることがある。そのような合材スラリー由来の各種配合成分の例として、増粘剤、(導電性)カーボンブラックおよび黒鉛などの公知の導電助剤、並びに、界面活性剤、分散剤、濡れ剤、消泡剤などその他の添加剤が挙げられる。これら各種配合成分の具体例は、次述する「合材層の形成方法」の項に記載されている。
本発明に係るリチウム電池用電極を構成する合材層は、水系合材スラリー(本明細書において、「合材スラリー」ともいう。)を作成した後、集電体(極板)の表面に該スラリーを塗布して、乾燥することによって製造することができる。この場合、合成スラリーには、上記活物質および水系接着剤が必須成分として含まれることになる。ここで、後述する本発明のリチウム電池用電極の製造方法においては、このように合材スラリーを極板表面に塗布して合材層を形成する工程は、合材層形成工程と呼ばれることがある。
本発明において、断熱層は、少なくとも熱活性化材料を含む。ここで、本発明のリチウム電池用電極において、前記合材層および断熱層の少なくとも一部が接触している。いいかえると、本発明のリチウム電池用電極において、断熱層は、その少なくとも一部が、前記合材層の少なくとも一部と接触している態様で存在する。本発明における典型的な態様においては、電極合材層(つまり、前記合材層)の表面に熱活性化材料を含む断熱層が形成される。
熱活性化材料としては、このような機能を発揮するとともに、本発明の機能を維持できる限り、熱活性化材料の材質には特に限定はないが、有機溶媒に可溶で水に膨潤しない窒素含有ポリマーであることが好ましい。
(ここで、室温の水に熱活性化材料Xgを添加して撹拌、ろ過した後の残渣の重さをYgとする)
そのような熱活性化材料として、たとえば、特開2012-134149号公報および特開2012-138359号公報に記載された熱活性化材料を使用することができる。すなわち、本発明で用いうる好適な窒素含有ポリマーは、数平均分子量が少なくとも1500の含窒素化合物、または数平均分子量が約200~2999の窒素含有オリゴマーを含む。1つの実施形態において、熱活性化材料は、窒素含有ポリマーを含み、窒素含有ポリマーは、アミン(amine)、アミド(amide)、イミド(imide)、マレイミド(maleimide)およびイミン(imine)から成る群より選ばれた1種類以上と、ジオン(dione)とが反応して形成されたハイパーブランチポリマー(hyper branched polymer)であってもよい。つまり、本発明の好適な態様において、窒素含有ポリマーは、アミン、アミド、イミド、マレイミドおよびイミンからなる群より選ばれた1種類以上ならびにジオン由来の成分を有する。ここで、窒素含有ポリマーを構成する、アミン、アミド、イミド、マレイミドおよびイミンの具体例として、特開2012-134149号公報に記載のものが挙げられる。さらに詳しく説明すると、ジオンは、バルビツール酸(barbituric acid)、バルビツール酸の誘導体、アセチルアセトン(acetylacetone)、またはアセチルアセトンの誘導体を含む。中でも、N,N'-ビスマレイミド-4,4'-ジフェニルメタン(BMI)などのビスマレイミドモノマーとバルビツール酸(BTA)とを含んで得られる窒素含有ポリマーが好ましい。
断熱層には、前記熱活性化材料の他に、目的に応じて、Al、Mg、Si、Zr、Ti、Zn、Li、Co、またはその酸化物、その水酸化物、その硫化物、その窒化物、そのハロゲン化物、などの無機材料、また、Li2CO3のようなリチウム含有塩、またはリチウム含有の酸化物、水酸化物、硫化物、窒化物、炭酸塩、ハロゲン化物を含んでいても良い。また、N-メチルピロリドン(NMP)、ジメチルホルムアミド(DMF)、ジメチルアセトアミド(DMAC)、ピロリドン、N-ドデシルピロリドンなどのようなブレンステッド塩基性溶媒もしくはγ-ブチロラクトン(GBL)などのようなブレンステッド中性溶媒またはこれら溶媒を組み合わせた溶媒に溶解もしくは分散しているポリフッ化ビニリデンなどの接着剤を含んでいても良い。
本発明において、電極合材層(つまり、前記合材層)の表面に断熱層を形成する方法は、特に制限されないが、塗工による方法が好ましい。ここで、本発明における典型的な態様において、断熱層の形成は、有機溶媒に溶解した熱活性化材料を前記合材層表面に塗布することによって行うことができる。この場合、塗布されたスラリーに含まれていた有機溶媒がその後蒸発することにより、熱活性化材料および任意で用いられるその他の成分の塗工が成立して、少なくとも熱活性化材料を含む断熱層が、前記合材層表面に形成されることになる。
本発明では、第二の発明として、リチウム電池用電極の製造方法も提供される。
活物質と水系接着剤とを含む合材スラリーを極板表面に塗布して合材層を形成する合材層形成工程と、
前記合材層の表面に熱活性化材料を含む断熱層を形成する断熱層形成工程と
をこの順で含む。
本発明では、第三の発明として、リチウム電池も提供される。
本発明に係るリチウム電池において、正極、例えば、上記正極板(a)として、上述した本発明に係るリチウム電池用電極が好適に用いられる。この場合、本発明に係るリチウム電池は、活物質として正極活物質を採用し、正極、例えば、上記正極板(a)として機能する上述したリチウム電池用電極を備えることになる。
本発明に係るリチウム電池において、負極、例えば、上記負極板(b)として、従来公知の構成の負極(あるいは、負極板)を用いることができるし、上述した本発明に係るリチウム電池用電極を用いることもできる。
本発明において、正極板と負極板の間にセパレータ(c)が配置される。材質としては、(微)多孔性ポリエチレン、(微)多孔性ポリプロピレン、テフロン(登録商標)フィルム、ポリアミドフィルム、ポリ塩化ビニルフィルム、ポリフッ化ビニリデンフィルム、ポリアニリンフィルム、ポリイミドフィルム、不織布、ポリエチレンテレフタラート、ポリスチレンセルロース、またはそれらポリマーを2つ以上組み合わせた多層複合構造体がある。また、熱安定性に優れる他の樹脂がコーティングされていても良い。また、負極板とセパレータの間に、耐熱性フィラーと接着剤を含む多孔質耐熱層が存在していてもよい。耐熱性フィラーとしては、アルミナ、シリカ、チタニア、ジルコニア、マグネシア、イットリアなどの無機酸化物、セラミックス、ガラスなどを用いることができる。これらは1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。接着剤としては、前記電極合材層の製造方法に記載の水系接着剤を含んだ水系溶媒以外にも、ポリフッ化ビニリデンなどの非水系バインダーを含んだ非水系溶媒を用いることもできる。耐熱性フィラーが100質量部に対して、接着剤0.5~20質量部(固形分換算)であることが好ましい。
正極板、負極板、セパレータ全体を電解液(d)が浸漬している。電解液としては、プロピレンカーボネート、エチレンカーボネート、γ-ブチロラクトン、ジメチルスルホキシド、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、1,2-ジメトキシエタン、1,2-ジエトキシエタン、テトラヒドロフラン等が挙げられ、いずれかが単独でまたは2種以上を混合して使用される。その電解液の中に、リチウム塩を溶解させる。リチウム塩としては、LiPF6、LiBF4、LiClO4、LiAsF6、CF3SO3Li、(CF3SO2)2N・Li等の電解質を、1種単独でまたは2種以上組み合わせて有機溶媒に溶解したものを使用することができる。電解液には、必要に応じて、ビニレンカーボネートや1,3-プロペンスルトン、リチウムビス(オキサレート)ボレート(LiBOB)、マレイミド系化合物などの添加剤を加えても良い。
リチウム電池の外装材としては、金属製の缶、例えば鉄、ステンレススチール、アルミニウムなどからなる缶が好ましい。また、極薄のアルミを樹脂でラミネートしたフィルム状の袋を使用しても構わない。外装材の形状は円筒型、角型、薄型、コイン型などいずれでも構わない。
<リチウム電池用水系正極板LiNi0.4Mn0.4Co0.2O2の作製>
(合材スラリーの調製)
LiNi0.4Mn0.4Co0.2O2 100重量部、導電性カーボンブラック(ティムカル社製SuperP)4.44重量部、黒鉛(ティムカル社製KS-6)2.22重量部、予め水に溶解させたカルボキシメチルセルロース(第一工業製薬(株)製WS-A)を固形分換算で1.11重量部、水に分散しているオレフィン系水系接着剤(三井化学(株)ケミパールEVS6500N)を固形分換算で4.44重量部を添加し、プラネタリーミキサーと高速攪拌機(井上製作所製)を用いて、合材スラリーを作成した。さらに粘度調整用に水を加えて分散調整した。
上記で得られた合材スラリーを用いて、正極板用集電体への合材スラリーの塗工、乾燥を行った。塗工、乾燥には、塗工機(井上金属工業(株)製)を使用した。3ゾーンある各乾燥ゾーンの水系スラリーの条件は、第1、2、3乾燥ゾーンそれぞれにおいて、60、90、120℃にて行った。風速は12m/sと設定した。正極板用集電体である厚さが20μmのアルミニウム箔に、合材スラリーを一方の面に塗布乾燥した。同様にして、他方の面にも塗布乾燥し、正極板用前駆電極とした。片面あたりの塗布量は、乾燥後で12mg/cm2とした。
(プレス工程)
作成した電極(すなわち、前記正極板用前駆電極)をロールプレス機で圧延し、正極板用圧延前駆電極とした。電極合材層の密度が3g/cm3になるように処理を行った。
(断熱層用の塗工液の作成)
N-メチルピロリドンを入れた1Lフラスコに、N,N'-bismaleimide-4,4'-diphenylmethane(Hakuei社製)とバルビツール酸(Hakuei社製)を2:1の比で添加して、130℃、48時間加熱攪拌した。得られた溶液を2%溶液に希釈した。
(断熱層の作製)
前記塗工機を用いて、断熱層用の塗工液をプレス工程まで終了した電極(すなわち、前記正極板用圧延前駆電極)上に塗工し、乾燥した。乾燥条件は、100、130、150℃にて行った。風速は12m/sと設定した。塗工時の膜厚が12.5μmとなるように塗工した。その結果、正極板が得られた。
[比較例1]
<リチウム電池用溶剤系正極板LiNi0.4Mn0.4Co0.2O2の作製>
LiNi0.4Mn0.4Co0.2O2 100重量部、導電性カーボンブラック(ティムカル社製SuperP)4.44重量部、黒鉛(ティムカル社製KS-6)2.22重量部、N-メチルピロリドンで溶解したPVDF(ポリフッ化ビニリデン、呉羽化学工業(株)製KFポリマーW1300)を固形分換算で4.44重量部を添加し、プラネタリーミキサーと高速攪拌機(井上製作所製)を用いて、合材スラリーを作成した。さらに粘度調整用にN-メチルピロリドンを加えて分散調整した。
断熱層の作製を行わないことを除き、実施例1および比較例1とそれぞれ同様に正極板を作成した。
<リチウム電池用水系正極板LiMn2O4の作製>
実施例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiMn2O4に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で20mg/cm2とした。プレス工程は、電極合材層の密度が2.5g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用溶剤系正極板LiMn2O4の作製>
比較例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiMn2O4に変更した。塗工も比較例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で20mg/cm2とした。プレス工程は、電極合材層の密度が2.5g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
断熱層の作製を行わないことを除き、実施例2および比較例2とそれぞれ同様に正極板を作成した。
<リチウム電池用水系正極板LiCoO2の作製>
実施例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiCoO2に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で15mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用溶剤系正極板LiCoO2の作製>
比較例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiCoO2に変更した。塗工も比較例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で15mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
断熱層の作製を行わないことを除き、実施例3および比較例3とそれぞれ同様に正極板を作成した。
<リチウム電池用水系正極板LiMn1.5Ni0.5O4の作製>
実施例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiMn1.5Ni0.5O4に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で15mg/cm2とした。プレス工程は、電極合材層の密度が2.5g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用溶剤系正極板LiMn1.5Ni0.5O4の作製>
比較例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiMn1.5Ni0.5O4に変更した。塗工も比較例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で15mg/cm2とした。プレス工程は、電極合材層の密度が2.5g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
断熱層の作製を行わないことを除き、実施例4および比較例4とそれぞれ同様に正極板を作成した。
<リチウム電池用水系正極板LiFePO4の作製>
実施例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiFePO4に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で16mg/cm2とした。プレス工程は、電極合材層の密度が2g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用溶剤系正極板LiFePO4の作製>
比較例1と同様の方法により、合材スラリーを作成した。活物質のみLiNi0.4Mn0.4Co0.2O2からLiFePO4に変更した。塗工も比較例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で16mg/cm2とした。プレス工程は、電極合材層の密度が2g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
断熱層の作製を行わないことを除き、実施例5および比較例5とそれぞれ同様に正極板を作成した。
<リチウム電池用水系正極板LiNi0.4Mn0.4Co0.2O2-ポリプロピレン系接着剤の作製>
実施例1と同様の方法により、合材スラリーを作成した。接着剤のみオレフィン系水系接着剤(三井化学(株)ケミパールEVS6500N)から、ポリプロピレン系接着剤に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で12mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用水系正極板LiNi0.4Mn0.4Co0.2O2-SBR接着剤の作製>
実施例1と同様の方法により、合材スラリーを作成した。接着剤のみオレフィン系水系接着剤(三井化学(株)ケミパールEVS6500N)から、SBR(スチレンーブタジエンラテックス)に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で12mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用水系正極板LiNi0.4Mn0.4Co0.2O2-アクリル系接着剤の作製>
実施例1と同様の方法により、合材スラリーを作成した。接着剤のみオレフィン系水系接着剤(三井化学(株)ケミパールEVS6500N)から、アクリル系接着剤(スチレンーメタクリル酸)に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で12mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用水系正極板LiNi0.4Mn0.4Co0.2O2-増粘剤ポリビニルアルコールの作製>
実施例1と同様の方法により、合材スラリーを作成した。増粘剤をカルボキシメチルセルロースからポリビニルアルコール((株)クラレ製KL-318)に変更した。塗工も実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で12mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<リチウム電池用水/有機溶剤混合系正極板LiNi0.4Mn0.4Co0.2O2の作製>
実施例1と同様の方法により、合材スラリーを作成した。溶媒の水に10%分イソプロピルアルコールを添加した。塗工は実施例1と同様の方法にて行った。片面あたりの塗布量は、乾燥後で12mg/cm2とした。プレス工程は、電極合材層の密度が3g/cm3になるように実施した。断熱層の塗工も実施例1と同様の方法にて行った。
<Al2O3含有断熱層の作成>
Al2O3 100重量部、N-メチルピロリドンで溶解したPVDF(呉羽化学工業(株)製KFポリマーW1300)を固形分換算で4.44重量部、N-メチルピロリドンに溶解した N,N'-bismaleimide-4,4'-diphenylmethaneとバルビツール酸から合成した溶液を添加し、プラネタリーミキサーと高速攪拌機(井上製作所製)を用いて、スラリーを作成した。さらに粘度調整用にN-メチルピロリドンを加えて分散調整した。その溶液を参考例1-1の正極板に塗工した。
実施例11と同様に作成したスラリーを参考例1-2の正極板に塗工した。
<Li2CO3含有断熱層の作成>
Li2CO3 100重量部、N-メチルピロリドンで溶解したPVDF(呉羽化学工業(株)製KFポリマーW1300)を固形分換算で4.44重量部、N-メチルピロリドンに溶解した N,N'-bismaleimide-4,4'-diphenylmethaneとバルビツール酸から合成した溶液を添加し、プラネタリーミキサーと高速攪拌機(井上製作所製)を用いて、スラリーを作成した。さらに粘度調整用にN-メチルピロリドンを加えて分散調整した。その溶液を参考例1-1の正極板に塗工した。
実施例12と同様に作成したスラリーを参考例1-2の正極板に塗工した。
<断熱層塗工後の正極板の評価>
断熱層塗工前後の正極板の厚みを測定し、膨潤具合を調べた。得られた結果をもとに、「実施例÷対応する参考例」によって、規格化した。結果を表1に示す。値が小さい程、膨潤が少ないことを示している。
得られた正極板を用いて、断熱層塗工後の極板を1.5cm×2cmの大きさに切り出し、瞬間接着剤にてガラスプレパラートに貼り付け電極を固定し評価用サンプルとした。評価用サンプルを塗膜剥離強度測定装置サイカスDN20型(ダイプラウインテス(株)製)で電極合材層と正極板の間を水平速度2μm/秒の速度で切削し、切削に必要な水平方向の力から電極合材層の剥離強度(kN/m)を測定した。得られた結果をもとに、「実施例÷対応する参考例」によって、規格化した。結果を表1に示す。値が大きい程、接着強度が強いことを示している。
<リチウム電池用負極板の作製>
(合材スラリーの調製)
メソフェーズグラファイト粉末94重量部、導電性カーボンブラック(ティムカル社製SuperP)1重量部、N-メチルピロリドンで溶解したPVDFを固形分換算で5重量部を添加し、プラネタリーミキサーと高速攪拌機(井上製作所製)を用いて、合材スラリーを作成した。さらに粘度調整用にN-メチルピロリドンを加えて分散調整した。
上記で得られた合材スラリーを用いて、正極板で用いた塗工機により、負極板用集電体への合材スラリーの塗工、乾燥を行った。3ゾーンある各乾燥ゾーンの条件は、100、110、120℃にて行った。風速は12m/sと設定した。負極板用集電体である厚さが10μmの銅箔に両面塗布乾燥し、負極板用前駆電極とした。片面あたりの塗布量は、乾燥後で11.3mg/cm2とした。
作成した電極(すなわち、前記負極板用前駆電極)をロールプレス機で圧延し、負極板とした。電極合材層の密度が1.5g/cm3になるように処理を行った。
非水溶媒として、エチレンカーボネート(EC)とメチルエチルカーボネート(MEC)を、EC:MEC=1:1(体積比)の割合で混合したものを用い、次に電解質であるLiPF6を溶解し電解質濃度が1.0モル/リットルとなるように非水電解液を調製した。
コイン型リチウム電池用の負極板として、上述の負極板を用いて、直径14mmの円盤状に打ち抜いて、コイン状の負極板を得た。得られた正極板を用いて、直径13.5mmの円盤状にうちぬき、コイン状の正極板をそれぞれ得た。コイン状の負極板、正極板、および微多孔性ポリエチレンフィルムのセパレータ(セルガード製)を、ステンレス製の2032サイズ電池缶の負極缶内に、負極板、セパレータ、正極板の順序で積層した。その後、セパレータに前記非水電解液0.04mlを注入した後に、その積層体の上にアルミニウム製の板(厚さ1.2mm、直径16mm)、およびバネを重ねた。最後に、ポリプロピレン製のガスケットを介して電池の正極缶をかぶせて、缶蓋をかしめることにより、電池内の気密性を保持し、直径20mm、高さ3.2mmのコイン型リチウム電池を作製した。
作製したコイン型リチウム電池を使用し、電池を0.1Cの定電流値で充電し、所定の電圧に達した後、電流値が0.05Cになるまで充電した。この時の充電容量を初期充電容量(mAh/g)とした。
Claims (7)
- 極板と、合材層と、断熱層とをこの順で備え、
前記合材層は少なくとも水系接着剤と活物質とを含み、
前記断熱層は少なくとも熱活性化材料を含み、かつ
前記合材層および前記断熱層の少なくとも一部が接触しているリチウム電池用電極。 - 前記熱活性化材料が、有機溶媒に可溶で水に膨潤しない窒素含有ポリマーである請求項1記載のリチウム電池用電極。
- 前記窒素含有ポリマーが、アミン、アミド、イミド、マレイミドおよびイミンからなる群より選ばれた1種類以上ならびにジオン由来の成分を有する請求項2記載のリチウム電池用電極。
- 前記水系接着剤が、オレフィン系樹脂またはアクリル系樹脂の少なくとも一つが水に分散または溶解したものである請求項1~3のいずれか一項に記載のリチウム電池用電極。
- 活物質と水系接着剤とを含む合材スラリーを極板表面に塗布して合材層を形成する合材層形成工程と、
前記合材層の表面に熱活性化材料を含む断熱層を形成する断熱層形成工程と
をこの順で含む、リチウム電池用電極の製造方法。 - 前記断熱層形成工程が、有機溶媒に溶解した熱活性化材料を前記合材層表面に塗布して断熱層を形成する工程である、請求項5に記載のリチウム電池用電極の製造方法。
- 請求項1~4のいずれか一項に記載のリチウム電池用電極を備える、リチウム電池。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020157022347A KR20150108400A (ko) | 2013-01-31 | 2014-01-28 | 리튬 전지용 전극 및 그 제조 방법, 및 리튬 전지 |
US14/764,902 US9941517B2 (en) | 2013-01-31 | 2014-01-28 | Electrode for lithium battery and production process thereof, and lithium battery |
JP2014559685A JP6192019B2 (ja) | 2013-01-31 | 2014-01-28 | リチウム電池およびその製造方法 |
EP14746495.2A EP2953194A4 (en) | 2013-01-31 | 2014-01-28 | ELECTRODE FOR LITHIUM BATTERIES, METHOD FOR THE MANUFACTURE THEREOF AND LITHIUM BATTERY |
CN201480005970.9A CN104956524B (zh) | 2013-01-31 | 2014-01-28 | 锂电池用电极及其制造方法、以及锂电池 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013016664 | 2013-01-31 | ||
JP2013-016664 | 2013-01-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014119554A1 true WO2014119554A1 (ja) | 2014-08-07 |
Family
ID=51262268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/051795 WO2014119554A1 (ja) | 2013-01-31 | 2014-01-28 | リチウム電池用電極およびその製造方法、並びにリチウム電池 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9941517B2 (ja) |
EP (1) | EP2953194A4 (ja) |
JP (1) | JP6192019B2 (ja) |
KR (1) | KR20150108400A (ja) |
CN (1) | CN104956524B (ja) |
TW (1) | TWI652847B (ja) |
WO (1) | WO2014119554A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016152152A (ja) * | 2015-02-18 | 2016-08-22 | 三井化学株式会社 | セパレータ及びその製造方法、リチウムイオン二次電池 |
JPWO2016052667A1 (ja) * | 2014-09-30 | 2017-05-18 | 三井化学株式会社 | リチウム電池用電極、リチウム電池、及び電気化学セル用ペースト |
JPWO2016063813A1 (ja) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | 二次電池用電極およびこれを用いた二次電池 |
CN107078338A (zh) * | 2014-10-22 | 2017-08-18 | 三井化学株式会社 | 锂二次电池 |
CN108352506A (zh) * | 2016-07-04 | 2018-07-31 | 株式会社Lg化学 | 正极和包含该正极的二次电池 |
US10326140B2 (en) | 2016-09-21 | 2019-06-18 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery, battery pack, and vehicle |
CN110311138A (zh) * | 2019-07-11 | 2019-10-08 | 安普瑞斯(无锡)有限公司 | 一种具有热动保护功能的锂离子二次电池 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6430472B2 (ja) * | 2016-01-15 | 2018-11-28 | 関西ペイント株式会社 | リチウムイオン電池正極用導電ペースト及びリチウムイオン電池正極用合材ペースト |
JP6680238B2 (ja) * | 2017-02-17 | 2020-04-15 | トヨタ自動車株式会社 | 電極体の製造方法 |
CN110462888B (zh) * | 2017-03-31 | 2022-08-26 | 松下知识产权经营株式会社 | 电化学装置用正极和具备其的电化学装置 |
CN109411769B (zh) * | 2018-10-26 | 2020-11-17 | 阜阳创启工艺品有限公司 | 一种燃料电池用长寿命碳纤维纸的制备方法 |
TWI752726B (zh) * | 2019-11-12 | 2022-01-11 | 財團法人工業技術研究院 | 鋰電池結構 |
CN115093131B (zh) * | 2022-06-30 | 2023-08-08 | 东海县亚连玻璃有限公司 | 一种具有隔热保温功能的镀膜玻璃及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001093583A (ja) * | 1998-11-16 | 2001-04-06 | Denso Corp | 積層型電池及びその電極の製造方法 |
JP2012134149A (ja) | 2010-12-23 | 2012-07-12 | Ind Technol Res Inst | リチウム電池および電極板構造 |
JP2012138359A (ja) | 2010-12-27 | 2012-07-19 | Ind Technol Res Inst | リチウム電池および電極板構造 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20030086354A (ko) | 2001-04-10 | 2003-11-07 | 미쓰비시 마테리알 가부시키가이샤 | 리튬 이온 폴리머 2차 전지, 그 전지용 전극 및 그 전지의밀착층에 사용하는 결착제 중의 고분자 화합물의 합성 방법 |
JP4602254B2 (ja) | 2003-09-18 | 2010-12-22 | パナソニック株式会社 | リチウムイオン二次電池 |
JP2006228515A (ja) * | 2005-02-16 | 2006-08-31 | Sii Micro Parts Ltd | 非水電解質二次電池 |
JP2010021113A (ja) | 2008-07-14 | 2010-01-28 | Panasonic Corp | リチウムイオン二次電池の製造法 |
WO2010032784A1 (ja) | 2008-09-18 | 2010-03-25 | 日本ゼオン株式会社 | 二次電池電極用バインダー組成物およびその製造方法 |
TWI411149B (zh) | 2008-12-31 | 2013-10-01 | Ind Tech Res Inst | 鋰電池及其製造方法 |
JP5412853B2 (ja) | 2009-01-30 | 2014-02-12 | ダイキン工業株式会社 | リチウム二次電池の正極の製造方法および正極ならびにリチウム二次電池 |
CN102318108A (zh) | 2009-02-12 | 2012-01-11 | 大金工业株式会社 | 锂二次电池的电极合剂用浆料、使用了该浆料的电极和锂二次电池 |
JP5553583B2 (ja) | 2009-11-30 | 2014-07-16 | ユニチカ株式会社 | 二次電池電極用バインダー、二次電池電極用バインダーを用いてなる電極及び二次電池 |
WO2012036260A1 (ja) | 2010-09-16 | 2012-03-22 | 日本ゼオン株式会社 | 二次電池用正極 |
-
2014
- 2014-01-28 JP JP2014559685A patent/JP6192019B2/ja active Active
- 2014-01-28 EP EP14746495.2A patent/EP2953194A4/en not_active Withdrawn
- 2014-01-28 CN CN201480005970.9A patent/CN104956524B/zh active Active
- 2014-01-28 US US14/764,902 patent/US9941517B2/en active Active
- 2014-01-28 WO PCT/JP2014/051795 patent/WO2014119554A1/ja active Application Filing
- 2014-01-28 KR KR1020157022347A patent/KR20150108400A/ko not_active Application Discontinuation
- 2014-01-29 TW TW103103429A patent/TWI652847B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001093583A (ja) * | 1998-11-16 | 2001-04-06 | Denso Corp | 積層型電池及びその電極の製造方法 |
JP2012134149A (ja) | 2010-12-23 | 2012-07-12 | Ind Technol Res Inst | リチウム電池および電極板構造 |
JP2012138359A (ja) | 2010-12-27 | 2012-07-19 | Ind Technol Res Inst | リチウム電池および電極板構造 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2953194A4 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2016052667A1 (ja) * | 2014-09-30 | 2017-05-18 | 三井化学株式会社 | リチウム電池用電極、リチウム電池、及び電気化学セル用ペースト |
CN107078275A (zh) * | 2014-09-30 | 2017-08-18 | 三井化学株式会社 | 锂电池用电极、锂电池以及电化学单体电池用糊料 |
EP3203547A4 (en) * | 2014-09-30 | 2018-05-02 | Mitsui Chemicals, Inc. | Electrode for lithium batteries, lithium battery and paste for electrochemical cells |
JPWO2016063813A1 (ja) * | 2014-10-21 | 2017-08-03 | 日本電気株式会社 | 二次電池用電極およびこれを用いた二次電池 |
CN107078338A (zh) * | 2014-10-22 | 2017-08-18 | 三井化学株式会社 | 锂二次电池 |
JP2016152152A (ja) * | 2015-02-18 | 2016-08-22 | 三井化学株式会社 | セパレータ及びその製造方法、リチウムイオン二次電池 |
CN108352506A (zh) * | 2016-07-04 | 2018-07-31 | 株式会社Lg化学 | 正极和包含该正极的二次电池 |
JP2018537815A (ja) * | 2016-07-04 | 2018-12-20 | エルジー・ケム・リミテッド | 正極及び前記正極を含む二次電池 |
US10622625B2 (en) | 2016-07-04 | 2020-04-14 | Lg Chem, Ltd. | Positive electrode and secondary battery including the same |
US10326140B2 (en) | 2016-09-21 | 2019-06-18 | Kabushiki Kaisha Toshiba | Nonaqueous electrolyte battery, battery pack, and vehicle |
CN110311138A (zh) * | 2019-07-11 | 2019-10-08 | 安普瑞斯(无锡)有限公司 | 一种具有热动保护功能的锂离子二次电池 |
Also Published As
Publication number | Publication date |
---|---|
KR20150108400A (ko) | 2015-09-25 |
TWI652847B (zh) | 2019-03-01 |
CN104956524A (zh) | 2015-09-30 |
US20150372307A1 (en) | 2015-12-24 |
JP6192019B2 (ja) | 2017-09-06 |
CN104956524B (zh) | 2018-11-27 |
US9941517B2 (en) | 2018-04-10 |
TW201444154A (zh) | 2014-11-16 |
EP2953194A1 (en) | 2015-12-09 |
EP2953194A4 (en) | 2016-08-24 |
JPWO2014119554A1 (ja) | 2017-01-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6192019B2 (ja) | リチウム電池およびその製造方法 | |
KR102303725B1 (ko) | 열가교형 리튬이온 전지용 슬러리 및 그 제조방법, 리튬이온 전지용 전극, 리튬이온 전지용 세퍼레이터, 리튬이온 전지용 세퍼레이터/전극적층체, 및 리튬이온 전지 | |
JP5652633B1 (ja) | リチウムイオン二次電池用組成物、リチウムイオン二次電池用スラリー、リチウムイオン二次電池用電極、リチウムイオン二次電池用セパレーターおよびリチウムイオン二次電池 | |
US10193117B2 (en) | Separator for nonaqueous secondary battery, and nonaqueous secondary battery | |
KR102165556B1 (ko) | 이차 전지용 세퍼레이터 | |
EP2696394B1 (en) | Nonaqueous secondary battery separator and nonaqueous secondary battery | |
JP5603522B2 (ja) | 非水電解質電池用セパレータおよび非水電解質電池 | |
JP2012109123A (ja) | 耐熱性微多孔膜および電池用セパレータ | |
TW201836850A (zh) | 多孔性薄膜、二次電池用隔離材及二次電池 | |
KR20160079623A (ko) | 이차 전지용 바인더, 이를 포함하는 이차 전지용 세퍼레이터 및 이를 포함하는 이차 전지 | |
WO2014021292A1 (ja) | 非水電解質電池用セパレータおよび非水電解質電池 | |
US20140312268A1 (en) | Battery binder | |
KR20200092310A (ko) | 전기 화학 소자용 도전재 페이스트, 전기 화학 소자 정극용 슬러리 조성물 및 그 제조 방법, 전기 화학 소자용 정극, 그리고 전기 화학 소자 | |
JP2015181110A (ja) | 耐熱性微多孔膜、リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池 | |
JP2006182925A (ja) | コアシェル型微粒子、および該微粒子を有するリチウム二次電池 | |
KR20190042842A (ko) | 이차전지용 분리막, 이의 제조방법 및 이를 포함하는 리튬 이차전지 | |
KR20160021771A (ko) | 축전 디바이스용 조성물, 축전 디바이스용 슬러리, 축전 디바이스 전극 및 그의 제조 방법, 보호막 및 그의 제조 방법, 및 축전 디바이스 | |
CN114725623A (zh) | 电池、电子设备、移动装置 | |
CN108352531B (zh) | 锂离子二次电池用电极 | |
JP6346959B2 (ja) | リチウム電池用電極、リチウム電池、及び電気化学セル用ペースト | |
CN114128028A (zh) | 用于电化学装置的复合隔板和包括该复合隔板的电化学装置 | |
JP2015041570A (ja) | リチウムイオン二次電池用多孔膜組成物、リチウムイオン二次電池用多孔膜、リチウムイオン二次電池、およびリチウムイオン二次電池用多孔膜の製造方法 | |
JP2022146804A (ja) | リチウムイオン二次電池用電極、その製造方法、スラリー組成物、及びリチウムイオン二次電池 | |
CN116315459A (zh) | 隔膜、电化学装置以及电子设备 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14746495 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014559685 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14764902 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: 2014746495 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20157022347 Country of ref document: KR Kind code of ref document: A |