JP4628007B2 - Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents
Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDFInfo
- Publication number
- JP4628007B2 JP4628007B2 JP2004102892A JP2004102892A JP4628007B2 JP 4628007 B2 JP4628007 B2 JP 4628007B2 JP 2004102892 A JP2004102892 A JP 2004102892A JP 2004102892 A JP2004102892 A JP 2004102892A JP 4628007 B2 JP4628007 B2 JP 4628007B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- carbon material
- negative electrode
- ion secondary
- lithium ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003575 carbonaceous material Substances 0.000 title claims description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 150000001247 metal acetylides Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 239000002243 precursor Substances 0.000 description 28
- 229910052751 metal Inorganic materials 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 239000011255 nonaqueous electrolyte Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 12
- 239000011245 gel electrolyte Substances 0.000 description 12
- -1 vacuum Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000007784 solid electrolyte Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 101100327917 Caenorhabditis elegans chup-1 gene Proteins 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000002180 crystalline carbon material Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002134 carbon nanofiber 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
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002641 tar oil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910015044 LiB Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013371 LiBrF4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013534 LiN(HCF2CF2CH2OSO2)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、リチウムイオン二次電池の負極に適した炭素材料、リチウムイオン二次電池用負極、および該負極を用いた放電容量、不可逆容量に優れたリチウムイオン二次電池に関する。 The present invention relates to a carbon material suitable for a negative electrode of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery excellent in discharge capacity and irreversible capacity using the negative electrode.
リチウムイオン二次電池は作動電圧が高いこと、電池容量が大きいことおよびサイクル寿命が長いなどの優れた特徴を有し、かつ環境汚染が少ないことから、従来主流であったニッケル・カドミウム電池やニッケル水素電池に代わって広範囲で用いられている。リチウムイオン二次電池が実用可能となったのは、負極材料として安全性に問題があったリチウム金属に代わり、リチウムイオンを層間挿入した炭素材料が安定した活物質となり得ることが発見され、リチウムイオン二次電池の実用化と性能向上に果たす炭素材料の役割が認識されたことに起因する。 Lithium-ion secondary batteries have excellent features such as high operating voltage, large battery capacity, long cycle life, and low environmental pollution. Therefore, conventional nickel-cadmium batteries and nickel It is widely used in place of hydrogen batteries. Lithium ion secondary batteries have become practical because it was discovered that carbon materials with intercalated lithium ions could be a stable active material instead of lithium metal, which had a safety problem as a negative electrode material. This is due to the recognition of the role of carbon materials in the practical application and performance improvement of ion secondary batteries.
近年の携帯電話やノートパソコンなどの携帯電子機器の高性能・高機能化に伴い消費電力が増加し、リチウムイオン二次電池のさらなる高容量化が求められている。リチウムイオン二次電池の容量は、特に負極用炭素材料の質量当りの放電容量が大きな支配要因であるが、質量当りの放電容量は炭素負極材料の中では高純度の天然黒鉛の理論容量３７２mAh/gが限界である。そのため、負極用炭素材料の放電容量をできるだけ天然黒鉛の理論容量に近づけることが試みられている。一方、リチウムイオン二次電池一本当りの放電容量を向上させるためには、体積当りの放電容量を向上させることも重要である。すなわち、負極板の電極密度を向上させ負極活物質をできるだけ多量に充填させることが重要である。しかし、質量当たりの放電容量が最も高いとされる天然黒鉛は、その鱗片状組織に由来し、電極密度を向上させようとすると、集電体に対して平行に配向するのでリチウムイオンの活物質内部への挿入が困難になる傾向があった。 With the recent increase in performance and functionality of portable electronic devices such as mobile phones and notebook computers, power consumption has increased, and further increase in capacity of lithium ion secondary batteries has been demanded. The capacity of the lithium ion secondary battery is particularly determined by the discharge capacity per mass of the carbon material for the negative electrode, but the discharge capacity per mass is the theoretical capacity of 372 mAh / g is the limit. For this reason, attempts have been made to make the discharge capacity of the carbon material for the negative electrode as close as possible to the theoretical capacity of natural graphite. On the other hand, in order to improve the discharge capacity per lithium ion secondary battery, it is also important to improve the discharge capacity per volume. That is, it is important to improve the electrode density of the negative electrode plate and to fill the negative electrode active material as much as possible. However, natural graphite, which is said to have the highest discharge capacity per mass, originates from its scaly structure, and when trying to improve the electrode density, it is oriented parallel to the current collector, so the active material of lithium ions There was a tendency for insertion into the interior to be difficult.
それを解決すべく、繊維状炭化物または塊状炭化物などを高結晶化する試みが行われてきた。例えば、硼素を触媒として黒鉛化し結晶構造の歪を矯正し高結晶化する方法が提案されている（特許文献１）。しかし、従来の硼素などの触媒を添加する方法は、触媒を炭化物あるいは炭化物前駆体に均一に混合するための制御が困難であることに加えて、触媒が高温熱処理時に酸化や窒化され、失活することを抑制する必要があった。それを回避するため、従来法では、過剰量の触媒を混合し、高温熱処理していた。しかし、高温熱処理後に、触媒が多量に残存し、得られた炭素材料を用いてなる負極では、リチウムイオン二次電池の電池特性に好ましくない影響を及ぼすという問題があった。 In order to solve this problem, attempts have been made to highly crystallize fibrous carbides or massive carbides. For example, a method of graphitizing using boron as a catalyst to correct the distortion of the crystal structure and highly crystallize has been proposed (Patent Document 1). However, the conventional method of adding a catalyst such as boron is difficult to control in order to uniformly mix the catalyst with the carbide or carbide precursor, and in addition, the catalyst is oxidized or nitrided during the high-temperature heat treatment and deactivated. There was a need to suppress it. In order to avoid this, in the conventional method, an excessive amount of catalyst is mixed and heat-treated at a high temperature. However, a large amount of catalyst remains after the high-temperature heat treatment, and the negative electrode using the obtained carbon material has a problem of adversely affecting the battery characteristics of the lithium ion secondary battery.
本発明は、微量の炭素を触媒として効果的に炭化物または炭化物前駆体に分散させることにより、高結晶性の炭素材料を製造し、得られた炭素材料を含有する負極を用いて、放電容量、不可逆容量などの充放電特性に優れたリチウムイオン二次電池を得ることが目的である。 The present invention produces a highly crystalline carbon material by effectively dispersing a minute amount of carbon in a carbide or carbide precursor as a catalyst, and using the obtained negative electrode containing the carbon material, the discharge capacity, The object is to obtain a lithium ion secondary battery excellent in charge / discharge characteristics such as irreversible capacity.
本発明は、鉄、コバルト、ニッケル、マンガン、白金、硼素および珪素からなる群から選ばれる少なくとも一種の元素、炭素繊維、カーボンナノチューブ、カーボンブラック、フラーレンまたは人造黒鉛である微小炭素、ならびにメソカーボン小球体の炭化物を含み、該微小炭素が該メソカーボン小球体の炭化物より小さく、該元素の微小炭素に対する割合が０．１〜１０質量％であり、該微小炭素の該メソカーボン小球体の炭化物に対する割合が０．０１〜３０質量％である組成物を、２０００℃以上で高温熱処理することを特徴とする炭素材料の製造方法である。 The present invention relates to at least one element selected from the group consisting of iron, cobalt, nickel, manganese, platinum, boron, and silicon , fine carbon that is carbon fiber, carbon nanotube, carbon black, fullerene, or artificial graphite , and small mesocarbon. include carbides of spheres, fine small carbon is smaller than the carbide of the mesocarbon spherules, the fraction is 0.1 to 10 mass% with respect to micro-carbon of said elements, for carbide of the mesocarbon spherules of the fine carbon A method for producing a carbon material, comprising subjecting a composition having a ratio of 0.01 to 30% by mass to heat treatment at a high temperature of 2000 ° C. or higher.
本発明の炭素材料の製造方法において、鉄、コバルト、ニッケル、マンガン、白金、硼素および珪素からなる群から選ばれる少なくとも一種の元素は、炭素繊維、カーボンナノチューブ、カーボンブラック、フラーレンおよび人造黒鉛から選ばれる少なくとも一種の微小炭素に含まれて使用されるのが好ましい。 In the method for producing a carbon material of the present invention, at least one element selected from the group consisting of iron, cobalt, nickel, manganese, platinum, boron and silicon is selected from carbon fiber, carbon nanotube, carbon black, fullerene and artificial graphite. It is preferable to be used by being contained in at least one kind of fine carbon.
本発明の炭素材料の製造方法において、微小炭素が、メソカーボン小球体の炭化物の表面に分散していることが好ましい。 In the method for producing a carbon material of the present invention, it is preferable that fine carbon is dispersed on the surface of the carbide of mesocarbon microspheres.
本発明の炭素材料の製造方法において、炭素材料が、リチウムイオン二次電池負極用炭素材料であることが好ましい。 In the carbon material production method of the present invention, the carbon material is preferably a carbon material for a negative electrode of a lithium ion secondary battery.
また、本発明は、前記いずれかの炭素材料の製造方法により製造された炭素材料を含有するリチウムイオン二次電池用負極である。 Moreover, this invention is a negative electrode for lithium ion secondary batteries containing the carbon material manufactured by the manufacturing method of one of the said carbon materials.
また、本発明は、前記リチウムイオン二次電池用負極を用いたリチウムイオン二次電池である。 Moreover, this invention is a lithium ion secondary battery using the said negative electrode for lithium ion secondary batteries.
本発明によれば、微量の金属元素、硼素および珪素からなる群から選ばれる少なくとも一種の元素を効果的に炭化物または炭化物前駆体に分散させることができるので、それら微量成分の黒鉛化物の高結晶化触媒としての作用を十分に発揮でき、高結晶性の炭素材料を得ることができる。該炭素材料を含む負極を用いると、放電容量、不可逆容量などの充放電特性に優れたリチウムイオン二次電池を得ることができる。 According to the present invention, at least one element selected from the group consisting of a trace amount of metal elements , boron and silicon can be effectively dispersed in the carbide or carbide precursor. The effect as a crystallization catalyst can be sufficiently exhibited, and a highly crystalline carbon material can be obtained. When a negative electrode containing the carbon material is used, a lithium ion secondary battery excellent in charge / discharge characteristics such as discharge capacity and irreversible capacity can be obtained.
（繊維状、球状または塊状の炭素）
本発明の炭素材料は、金属元素、硼素および珪素からなる群から選ばれる少なくとも一種の元素である微量成分、繊維状、球状または塊状の炭素と、メソカーボン小球体などの炭化物またはその前駆体とを高温熱処理した組成物である。
繊維状、球状または塊状の炭素は、カーボンナノチューブなどの繊維状黒鉛化物、カーボンブラック、フラーレンなどの球状黒鉛化物、または人造黒鉛などの塊状黒鉛化物である。該黒鉛化物は、炭化物または炭化物前駆体に対する割合が小さくても最大限の効果を発揮できるように、微小であることが好ましく（以後、微小炭素とも称す）、後述する炭化物または炭化物前駆体の大きさより小さいことが好ましい。該炭素の最大長は、好ましくは２０μｍ以下、より好ましくは５０ｎｍ〜２０μｍ、さらに好ましくは１００ｎｍ〜２０μｍである。微小炭素の大きさが２０μｍを超えると、炭化物または炭化物前駆体の黒鉛化物の表面に十分に融合しない場合がある。その形状は、繊維状、球状、塊状でなければならない。それ以外の形状の場合には、炭化物または炭化物前駆体に対する分散が十分でなく、期待する触媒作用が十分に発揮されない。
(Fibrous, spherical or massive carbon)
The carbon material of the present invention includes a trace component, fibrous, spherical, or massive carbon that is at least one element selected from the group consisting of a metal element , boron, and silicon, a carbide such as a mesocarbon microsphere, or a precursor thereof. Is a composition that has been heat-treated at a high temperature.
The fibrous, spherical, or massive carbon is a fibrous graphitized material such as carbon nanotube, a spherical graphitized material such as carbon black or fullerene, or a massive graphitized material such as artificial graphite. The graphitized material is preferably fine (hereinafter also referred to as fine carbon) so that the maximum effect can be exhibited even if the ratio to the carbide or the carbide precursor is small, and the size of the carbide or carbide precursor described later is large. It is preferable to be smaller. The maximum length of the carbon is preferably 20 μm or less, more preferably 50 nm to 20 μm, and still more preferably 100 nm to 20 μm. If the size of the minute carbon exceeds 20 μm, it may not be sufficiently fused to the surface of the graphitized material of the carbide or carbide precursor. The shape must be fibrous, spherical, or massive. In the case of other shapes, the dispersion to the carbide or carbide precursor is not sufficient, and the expected catalytic action is not sufficiently exhibited.
前記炭素の炭化物および／またはその前駆体の合計に対する配合割合は０．０１〜３０質量％、好ましくは０．０１〜２０質量％、さらに好ましくは０．１〜７質量％である。０．０１〜３０質量％にすることにより、後述する金属元素、硼素または珪素を含有する微小炭素が、炭化物および／またはその前駆体の表面に適度に分散し、高温熱処理の際に、炭化物の高結晶化が促進され、これを用いたリチウムイオン二次電池用負極を高容量化できる。
カーボンブラック、カーボンナノチューブ、気相成長炭素繊維などの微小炭素は、その生成過程で使用され、残存する金属元素や硼素、珪素などを微量含有しているので、本発明の原料として好都合である。特に好ましいのは、金属元素などを確実に微量含有する、精製前のカーボンブラックやカーボンナノチューブ、気相成長炭素繊維である。
The blending ratio of the carbon carbide and / or its precursor is 0.01 to 30% by mass, preferably 0.01 to 20% by mass, and more preferably 0.1 to 7% by mass. By setting the content to 0.01 to 30% by mass, fine carbon containing a metal element , boron or silicon, which will be described later, is appropriately dispersed on the surface of the carbide and / or its precursor. High crystallization is promoted, and the capacity of a negative electrode for a lithium ion secondary battery using the same can be increased.
Microcarbons such as carbon black, carbon nanotubes, and vapor-grown carbon fibers are used in the production process, and contain a trace amount of remaining metal elements , boron, silicon, and the like, which is advantageous as a raw material of the present invention. Particularly preferred are carbon black, carbon nanotubes, and vapor grown carbon fibers before purification that contain a trace amount of metal elements and the like.
（金属元素、硼素、珪素）
金属元素や硼素、珪素などの微量成分は、炭化物または炭化物前駆体を高温熱処理して黒鉛化する際に、炭化物または黒鉛化物の高結晶化に触媒的に作用し、高温熱処理後は、揮発するので、該微量成分を含有する炭素材料から作製したリチウムイオン二次電池用負極であっても、Ｌｉ合金化、すなわち、リチウムイオンの吸蔵・脱離に影響することはない。そして、黒鉛化物が高結晶性であると、黒鉛化物の結晶構造に歪がなく、リチウムイオンが黒鉛構造に入り込むことができるので、放電容量の増大に貢献する。金属元素などの微量成分は、微小炭素と併用することにより、該微量成分が、炭化物またはその前駆体に良好に分散する。
金属元素としては鉄、コバルト、ニッケル、マンガンなどの遷移金属や白金が好ましく、特に鉄とコバルトが好ましい。金属元素は２種以上を併用することもできる。金属元素と硼素および／または珪素を併用することもできる。その組成割合は問わない。
金属元素などの微量成分の微小炭素に対する割合は０．１〜１０質量％、好ましくは１〜１０質量％である。
(Metal elements , boron, silicon)
Trace elements such as metallic elements , boron and silicon act catalytically on high crystallization of carbides or graphitized materials when graphitizing carbides or carbide precursors by high-temperature heat treatment, and volatilize after high-temperature heat treatments. Therefore, even a negative electrode for a lithium ion secondary battery produced from a carbon material containing the trace component does not affect Li alloying, that is, occlusion / desorption of lithium ions. If the graphitized material is highly crystalline, the crystal structure of the graphitized material is not distorted and lithium ions can enter the graphite structure, which contributes to an increase in discharge capacity. When a trace component such as a metal element is used together with a minute carbon, the trace component is favorably dispersed in the carbide or its precursor.
As the metal element , transition metals such as iron, cobalt, nickel and manganese and platinum are preferable, and iron and cobalt are particularly preferable. Two or more metal elements can be used in combination. A metal element and boron and / or silicon can be used in combination. The composition ratio does not matter.
The ratio of a trace component such as a metal element to the minute carbon is 0.1 to 10% by mass, preferably 1 to 10% by mass.
金属元素や硼素、珪素などの微量成分は、前述した該微量成分を含有する微小炭素を、炭化物および／または炭化物前駆体に混合する方法、または該微量成分を微小炭素、炭化物および／または炭化物前駆体に混合する方法によって、本発明の組成物を調製する。これらの微量成分の配合効果を最大限に活かすためには、該微量成分を含む微小炭素を用いることが好ましい。 The trace component such as metal element , boron, silicon, etc. is a method of mixing the aforementioned minute carbon containing the trace component with the carbide and / or carbide precursor, or the trace component is added to the minute carbon, carbide and / or carbide precursor. The composition of the present invention is prepared by a method of mixing with the body. In order to maximize the blending effect of these trace components, it is preferable to use a minute carbon containing the trace component.
（炭化物および／またはその前駆体）
本発明の炭素材料の主原料となる炭化物および／または炭化物前駆体としては、塊状、繊維状の炭化物および／またはその前駆体が好ましく用いられる。鱗片状の物質や、光学顕微鏡で観察される流れ組織を有しない物質は好ましくない。炭化物および／または炭化物前駆体としては、炭素繊維、ピッチコークス、メソカーボン小球体炭化物などの炭化物、メソカーボン小球体などの炭化物前駆体が例示されるが、好適例は炭素繊維、メソカーボン小球体などの炭化物である。炭化物またはその前駆体の大きさ（長さ）は、前記の微小炭素より大きいことが好ましく、１０〜１００μｍが好ましく、１５〜７０μｍがより好ましく、２０〜７０μｍであることがさらに好ましい。
(Carbide and / or its precursor)
As the carbide and / or carbide precursor as the main raw material of the carbon material of the present invention, massive and fibrous carbides and / or precursors thereof are preferably used. A scale-like substance or a substance having no flow structure observed with an optical microscope is not preferable. Examples of carbides and / or carbide precursors include carbon fibers, pitch cokes, carbides such as mesocarbon microsphere carbides, and carbide precursors such as mesocarbon microspheres. Preferred examples include carbon fibers and mesocarbon microspheres. Such as carbides. The size (length) of the carbide or its precursor is preferably larger than the above-mentioned fine carbon, preferably 10 to 100 μm, more preferably 15 to 70 μm, and further preferably 20 to 70 μm.
（炭素材料）
本発明の炭素材料は、金属元素、硼素および珪素からなる群から選ばれる微量成分、微小炭素と、炭化物またはその前駆体を混合し、ろ過分離し、高温熱処理して製造される。本発明の炭素材料は、炭化物またはその前駆体に基づく黒鉛化物の粒子の周辺に、微小炭素に基づく黒鉛化物が融合しており、従来の微小炭素を含む炭化物からの炭素材料とは構造的に相違する。金属元素、硼素または珪素は揮発して、炭素材料には事実上残存しない。
該混合時、微小炭素および微量成分は、炭化物および／または炭化物前駆体に均一に分散していることが好ましい。そのため、通常、アセトン、トルエン、タール中油などの有機溶媒中で、微小炭素、微量成分、ならびに炭化物および／または炭化物前駆体を攪拌混合し、均一分散させた後、有機溶媒から固体をろ過分離することにより炭素材料を製造する方法が有効である。攪拌混合時に、１００〜３００℃に加熱して、ろ過後、炭化物および／またはその前駆体を焼成してもよい。焼成により有機溶媒などからなる揮発分の含有量を適度に調整することができる。
(Carbon material)
The carbon material of the present invention is produced by mixing a trace component selected from the group consisting of a metal element , boron and silicon, a minute carbon, and a carbide or a precursor thereof, separating by filtration, and heat-treating at a high temperature. In the carbon material of the present invention, the graphitized material based on the fine carbon is fused around the particle of the graphitized material based on the carbide or its precursor, and the carbon material from the carbide containing the conventional minute carbon is structurally different. Is different. The metal element , boron or silicon is volatilized and practically does not remain in the carbon material.
At the time of mixing, it is preferable that the fine carbon and the trace component are uniformly dispersed in the carbide and / or the carbide precursor. For this reason, usually, in an organic solvent such as acetone, toluene, or tar oil, fine carbon, trace components, and carbides and / or carbide precursors are stirred and mixed to uniformly disperse, and then the solid is filtered and separated from the organic solvent. Thus, a method for producing a carbon material is effective. At the time of stirring and mixing, the carbide and / or precursor thereof may be fired after heating to 100 to 300 ° C. and after filtration. The content of a volatile component composed of an organic solvent or the like can be appropriately adjusted by firing.
微小炭素、微量成分、ならびに炭化物および／または炭化物前駆体の混合比率は、前述した通り微小炭素の炭化物および／または炭化物前駆体との合計に対する割合を０．０１〜３０質量％、金属元素などの微量成分の微小炭素に対する割合を０．１〜１０質量％とすることが好ましい。
均一分散液からろ過により、固体である炭素材料を分離する。得られた炭素材料を金属元素、硼素または珪素が酸化しない程度の温度、例えば５０〜１２０℃で真空乾燥または窒素雰囲気で熱風乾燥すれば、次の高温熱処理に供することができる。
Fine carbon, trace components, and mixing ratio of the carbide and / or carbide precursors, 0.01 to 30% by weight ratio to the total of the carbide and / or carbide precursor as fine carbon described above, such metal elements The ratio of the trace component to the minute carbon is preferably 0.1 to 10% by mass.
A solid carbon material is separated from the uniform dispersion by filtration. If the obtained carbon material is dried at a temperature at which the metal element , boron or silicon is not oxidized, for example, vacuum drying at 50 to 120 ° C. or hot air drying in a nitrogen atmosphere, it can be subjected to the following high-temperature heat treatment.
前記乾燥後の炭素材料の高温熱処理は、真空、窒素雰囲気またはアルゴン雰囲気などの非酸化性雰囲気中で実施することが好ましい。例えば、タンマン炉またはアチソン炉により２０００℃以上の高温で加熱することが好ましく、より好ましくは２８００℃以上、最も好ましくは３０００℃近辺で加熱する。高温熱処理により、炭化物および／またはその前駆体から高結晶性の黒鉛化物が得られる。その際、金属元素などの微量成分が触媒として作用する。微小炭素は高温熱処理により結晶性の高い黒鉛化物になる。 The high-temperature heat treatment of the carbon material after drying is preferably performed in a non-oxidizing atmosphere such as vacuum, nitrogen atmosphere or argon atmosphere. For example, it is preferable to heat at a high temperature of 2000 ° C. or higher by a Tamman furnace or an Atchison furnace, more preferably 2800 ° C. or higher, and most preferably around 3000 ° C. By high-temperature heat treatment, highly crystalline graphitized material is obtained from carbide and / or its precursor. At that time, a trace component such as a metal element acts as a catalyst. Fine carbon becomes a graphitized material with high crystallinity by high-temperature heat treatment.
高温熱処理により得られた炭素材料は、下記する方法により、負極合剤ペーストに調製され、さらに、負極、リチウムオン二次電池が作製される。
リチウムイオン二次電池は、本質的に、充放電時にはリチウムイオンが負極中に吸蔵され、放電時には負極から脱離する電池機構である。リチウムイオン二次電池は、通常、負極、正極および非水電解質を主たる電池構成要素とし、正・負極はそれぞれリチウムイオンの担持体からなり、充放電過程における非水溶媒の出入りは層間で行われる。
本発明のリチウムイオン二次電池は、負極材料として前記高結晶性炭素材料を用いること以外は特に限定されず、他の電池構成要素については一般的なリチウムイオン二次電池の要素に準ずる。リチウムイオン二次電池は、通常、負極、正極および非水電解質を主たる電池構成要素とする。
The carbon material obtained by the high-temperature heat treatment is prepared into a negative electrode mixture paste by the following method, and further, a negative electrode and a lithium-on secondary battery are produced.
The lithium ion secondary battery is essentially a battery mechanism in which lithium ions are occluded in the negative electrode during charge / discharge and are detached from the negative electrode during discharge. A lithium ion secondary battery usually has a negative electrode, a positive electrode, and a nonaqueous electrolyte as main battery components, and the positive and negative electrodes are each composed of a lithium ion carrier, and the nonaqueous solvent enters and exits between layers in the charge / discharge process. .
The lithium ion secondary battery of the present invention is not particularly limited except that the highly crystalline carbon material is used as the negative electrode material, and other battery components conform to the elements of a general lithium ion secondary battery. A lithium ion secondary battery usually includes a negative electrode, a positive electrode, and a nonaqueous electrolyte as main battery components.
前記炭素材料からの負極の作製は、通常の作製方法に準じて行うことができるが、炭素材料の性能を十分に引出し、かつ粉末に対する成形性が高く、化学的、電気化学的に安定な負極を得ることができる方法であれば何ら制限されない。
負極作製時には、炭素材料に結合剤を加えた負極合剤を用いることができる。結合剤としては、電解質に対して化学的安定性、電気化学的安定性を有するものを用いることが好ましく、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレンなどのフッ素系樹脂、ポリエチレン、ポリビニルアルコール、カルボキシメチルセルロース、スチレンブタジエンラバーなどが用いられる。これらを併用することもできる。
The negative electrode can be produced from the carbon material in accordance with a normal production method, but the negative electrode is capable of sufficiently drawing out the performance of the carbon material and having high moldability to powder, and is chemically and electrochemically stable. There is no limitation as long as it can be obtained.
When preparing the negative electrode, a negative electrode mixture obtained by adding a binder to a carbon material can be used. As the binder, those having chemical stability and electrochemical stability with respect to the electrolyte are preferably used. For example, fluorine resins such as polyvinylidene fluoride and polytetrafluoroethylene, polyethylene, polyvinyl alcohol, carboxy Methyl cellulose, styrene butadiene rubber or the like is used. These can also be used together.
なお本発明では、負極材料に前記炭素材料を用いることにより、有機溶媒に溶解または分散する有機溶媒系結合剤はもちろんのこと、水溶性および／または水分散性の水系結合剤を用いても優れた充放電特性を発現する負極を得ることができる。
中でも、本発明の目的を達成し、効果を最大限に活かす上で、ポリフッ化ビニリデンなどの有機溶媒系結合剤を用いることが好ましい。
結合剤は、通常、負極合剤全量中０．５〜２０質量％程度の量で用いることが好ましい。具体的には、例えば、炭素材料を分級等によって適当な粒径に調整し、結合剤と混合することによって負極合剤を調整し、この負極合剤を、通常、集電体の片面あるいは両面に塗布することで負極合剤層を形成することができる。
In the present invention, by using the carbon material as the negative electrode material, not only an organic solvent-based binder that dissolves or disperses in an organic solvent but also a water-soluble and / or water-dispersible water-based binder can be used. In addition, a negative electrode that exhibits excellent charge / discharge characteristics can be obtained.
Among them, it is preferable to use an organic solvent-based binder such as polyvinylidene fluoride in order to achieve the object of the present invention and maximize the effect.
In general, the binder is preferably used in an amount of about 0.5 to 20% by mass in the total amount of the negative electrode mixture. Specifically, for example, the carbon material is adjusted to an appropriate particle size by classification or the like, and the negative electrode mixture is adjusted by mixing with a binder, and this negative electrode mixture is usually used on one or both sides of the current collector. The negative electrode mixture layer can be formed by applying to the substrate.
この際、通常の溶媒を用いることができ、負極合剤を溶媒中に分散させ、ペースト状とした後、集電体に塗布、乾燥すれば、負極合剤層が均一かつ強固に集電体に接着される。より具体的には、例えば、炭素材料と、ポリテトラフルオロエチレンなどのフッ素系樹脂粉末とを、イソプロピルアルコールなどの溶媒中で混合・混練した後、塗布すればよい。また炭素材料と、ポリフッ化ビニリデンなどのフッ素系樹脂、またはカルボキシメチルセルロース、スチレンブタジエンラバーなどを、N-メチルピロリドン、ジメチルホルムアミド、水、アルコール等の溶媒と混合してスラリーとした後、塗布することができる。
ペーストは、公知の攪拌機、混合機、混練機、ニーダーなどを用いて攪拌することにより調製することができる。
炭素材料と結合剤の混合物を集電体に塗布する際の塗布厚は１０〜２００μｍとするのが適当である。負極合剤層を形成した後、プレス加圧などの圧着を行うと、負極合剤層と集電体との接着強度をさらに高めることができる。
At this time, a normal solvent can be used, and the negative electrode mixture is dispersed in the solvent to form a paste, and then applied to the current collector and dried. Glued to. More specifically, for example, a carbon material and a fluorine resin powder such as polytetrafluoroethylene may be mixed and kneaded in a solvent such as isopropyl alcohol and then applied. Also, apply a carbon material and fluororesin such as polyvinylidene fluoride, or carboxymethyl cellulose, styrene butadiene rubber, etc. to a slurry by mixing with a solvent such as N-methylpyrrolidone, dimethylformamide, water, alcohol, etc. Can do.
The paste can be prepared by stirring using a known stirrer, mixer, kneader, kneader or the like.
The coating thickness when the mixture of the carbon material and the binder is applied to the current collector is suitably 10 to 200 μm. When the negative electrode mixture layer is formed and then pressure bonding such as pressurization is performed, the adhesive strength between the negative electrode mixture layer and the current collector can be further increased.
また、本発明の炭素材料と、ポリエチレン、ポリビニルアルコールなどの樹脂粉末とを乾式混合し、金型内でホットプレス成形して、負極を作製することもできる。
負極に用いる集電体の形状としては、特に限定されないが、箔状、あるいはメッシュ、エキスパンドメタルなどの網状のものなどが挙がられる。集電体としては、例えば、銅、ステンレス、ニッケルなどを挙げることができる。集電体の厚みは、箔状の場合、５〜２０μｍ程度が好適である。
The carbon material of the present invention and resin powder such as polyethylene and polyvinyl alcohol can be dry-mixed and hot press molded in a mold to produce a negative electrode.
The shape of the current collector used for the negative electrode is not particularly limited, and examples thereof include a foil shape or a net shape such as a mesh or an expanded metal. Examples of the current collector include copper, stainless steel, and nickel. In the case of a foil shape, the thickness of the current collector is preferably about 5 to 20 μm.
正極の材料（正極活物質）としては、充分量のリチウムを吸蔵・脱離しうるものを選択することが好ましい。そのような正極活物質としては、リチウム含有遷移金属酸化物、遷移金属カルコゲン化物、バナジウム酸化物（V2O5、V6O13、V2O4、V3O8など）およびリチウム化合物などのリチウム含有化合物、一般式MXMo6S8-Y（式中Xは0≦X≦4、Yは0≦Y≦1の範囲の数値であり、Mは遷移金属などの金属を表す）で表されるシェブレル相化合物、活性炭、活性炭素繊維などを用いることができる。
前記リチウム含有遷移金属酸化物は、リチウムと遷移金属との複合酸化物であり、リチウムと2種類以上の遷移金属を固溶したものであってもよい。リチウム含有遷移金属酸化物は、具体的には、LiM（１）1-XM（2）XO2（式中Xは0≦X≦1の範囲の数値であり、M（1）、M（2）は少なくとも一種類の遷移金属を表す）またはLIM（1）2-YM（2）YO4（式中Yは0≦Y≦1の範囲の数値であり、M（1）、M（2）は少なくとも一種の遷移金属を表す）で示される。
前記のMで示される遷移金属元素としては、Co、Ni、Mn、Cr、Ti、V、Fe、Zn、Al、In、Snなどが挙げられ、好ましくはCo、Fe、Mn、Ti、Cr、V、Alが挙げられる。
リチウム含有遷移金属酸化物としては、より具体的に、LiCoO2、LiXNiYM1-YO2（MはNiを除く遷移金属元素、好ましくはCo、Fe、Mn、Ti、Cr、V、Alから選ばれる少なくとも一種、0.05≦X≦1.10、0.5≦Y≦1.0である）で示されるリチウム複合酸化物、LiNiO2、LiMnO2、LiMn2O4などが挙げられる。
As the positive electrode material (positive electrode active material), it is preferable to select a material capable of inserting and extracting a sufficient amount of lithium. Examples of such positive electrode active materials include lithium-containing transition metal oxides, transition metal chalcogenides, vanadium oxides (V 2 O 5 , V 6 O 13 , V 2 O 4 , V 3 O 8, etc.) and lithium compounds. Lithium-containing compound of general formula M X Mo 6 S 8-Y (where X is a numerical value in the range of 0 ≦ X ≦ 4, Y is 0 ≦ Y ≦ 1, and M represents a metal such as a transition metal) A chevrel phase compound represented by the formula, activated carbon, activated carbon fiber and the like can be used.
The lithium-containing transition metal oxide is a composite oxide of lithium and a transition metal, and may be a solid solution of lithium and two or more transition metals. Specifically, the lithium-containing transition metal oxide is LiM (1) 1-X M (2) X O 2 (where X is a numerical value in the range of 0 ≦ X ≦ 1, M (1), M (2) represents at least one transition metal) or LIM (1) 2-Y M (2) Y O 4 (where Y is a numerical value in the range 0 ≦ Y ≦ 1, M (1), M (2) represents at least one transition metal).
Examples of the transition metal element represented by M include Co, Ni, Mn, Cr, Ti, V, Fe, Zn, Al, In, Sn, etc., preferably Co, Fe, Mn, Ti, Cr, V and Al are mentioned.
More specifically, as the lithium-containing transition metal oxide, LiCoO 2 , Li X Ni Y M 1-Y O 2 (M is a transition metal element excluding Ni, preferably Co, Fe, Mn, Ti, Cr, V , At least one selected from Al, 0.05 ≦ X ≦ 1.10, 0.5 ≦ Y ≦ 1.0), LiNiO 2 , LiMnO 2 , LiMn 2 O 4 and the like.
前記のようなリチウム含有遷移金属酸化物は、例えば、Ｌｉ、遷移金属の酸化物または塩類を出発原料とし、これら出発原料を組成に応じて混合し、酸素雰囲気下６００〜１０００℃の温度範囲で焼成することにより得ることができる。なお、出発原料は酸化物または塩類に限定されず、水酸化物などからも合成可能である。 The lithium-containing transition metal oxide as described above, for example, uses Li, transition metal oxides or salts as starting materials, and mixes these starting materials according to the composition, and in a temperature range of 600 to 1000 ° C. in an oxygen atmosphere. It can be obtained by firing. Note that the starting materials are not limited to oxides or salts, and can be synthesized from hydroxides or the like.
本発明では、正極活物質は、前記化合物を単独で使用しても２種類以上併用してもよい。例えば、正極中には、炭酸リチウムなどの炭素塩を添加することもできる。
このような正極材料によって正極を形成するには、例えば、正極材料と結合剤および電極に導電性を付与するための導電剤よりなる正極合剤を集電体の両面に塗布することで正極合剤層を形成する。結合剤としては、負極で例示したものがいずれも使用可能である。導電剤としては、例えば、黒鉛質粒子が用いられる。
In the present invention, the positive electrode active material may be used alone or in combination of two or more. For example, a carbon salt such as lithium carbonate can be added to the positive electrode.
In order to form a positive electrode with such a positive electrode material, for example, a positive electrode mixture comprising a positive electrode material, a binder, and a conductive agent for imparting conductivity to the electrode is applied to both sides of the current collector. An agent layer is formed. As the binder, any of those exemplified for the negative electrode can be used. As the conductive agent, for example, graphite particles are used.
集電体の形状は特に限定されず、箔状またはメッシュ、エキスパンドメタルなどの網状などのものが用いられる。例えば、集電体としては、アルミニウム、ステンレス、ニッケルなどを挙げることができる。その厚さとしては、１０〜４０μｍのものが好適である。 The shape of the current collector is not particularly limited, and a foil shape or a mesh shape such as a mesh or an expanded metal is used. For example, examples of the current collector include aluminum, stainless steel, and nickel. The thickness is preferably 10 to 40 μm.
また正極の場合も負極と同様に、正極合剤を溶剤中に分散させることでペースト状にし、このペースト状の正極合剤を集電体に塗布、乾燥することによって正極合剤層を形成してもよく、正極合剤を形成した後、さらにプレス加圧などの圧着を行ってもよい。これにより正極合剤層が均一かつ強固に集電体に接着される。
以上のような負極および正極を形成するに際しては、従来公知の導電剤や結着剤などの各種添加剤を適宜使用することができる。
Also in the case of the positive electrode, like the negative electrode, the positive electrode mixture is dispersed in a solvent to form a paste, and the paste-like positive electrode mixture is applied to a current collector and dried to form a positive electrode mixture layer. Alternatively, after forming the positive electrode material mixture, press bonding such as pressurization may be further performed. Thereby, the positive electrode mixture layer is uniformly and firmly bonded to the current collector.
In forming the negative electrode and the positive electrode as described above, conventionally known various additives such as a conductive agent and a binder can be appropriately used.
本発明に用いられる電解質としては通常の非水電解液に使用されている電解質塩を用いることができ、例えばLiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)、LiCl、LiBr、LiCF3SO3、LiCH3SO3、LiN(CF3SO2)、LiC(CF3SO2)3、LiN(CF3CH2OSO2)2、LiN(HCF2CF2CH2OSO2)2、LiN［(CF3)2CHOSO2］2、LiB[C6H3(CF3)2]４、LiAlCl4、LiSiF6などのリチウム塩を用いることができる。特に、LiPF6、LiBrF4が酸化安定性の点から好ましく用いられる。
電解液中の電解質濃度は、０．１〜５mol/Lが好ましく、０．５〜３．０mol/Lがより好ましい。
As the electrolyte used for the present invention can be used an electrolyte salt used in the conventional non-aqueous electrolyte solution, for example LiPF 6, LiBF 4, LiAsF 6 , LiClO 4, LiB (C 6 H 5), LiCl, LiBr, LiCF 3 SO 3 , LiCH 3 SO 3 , LiN (CF 3 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (HCF 2 CF 2 CH 2 OSO 2 ) 2 , LiN [(CF 3 ) 2 CHOSO 2 ] 2 , LiB [C 6 H 3 (CF 3 ) 2 ] 4 , LiAlCl 4 , LiSiF 6 and other lithium salts can be used. In particular, LiPF6 and LiBrF4 are preferably used from the viewpoint of oxidation stability.
0.1-5 mol / L is preferable and, as for the electrolyte concentration in electrolyte solution, 0.5-3.0 mol / L is more preferable.
上記非水電解質は、液系の非水電解液としてもよいし、固体電解質またはゲル電解質などの高分子電解質としてもよい。前者の場合、非水系電解質電池は、いわゆるリチウムイオン電池として構成され、後者の場合、非水電解質電池は、高分子固体電解質電池、高分子ゲル電解質電池などの高分子電解質電池として構成される。
液系の非水電解液とする場合には、溶媒として、エチレカーボネート、プロピレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、1,1-または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、2-メチルタトラヒドロフラン、γ-ブチルラクトン、1,3-ジオキソラン、4-メチル-1,3-ジオキソラン、アニソール、ジエチルエーテル、スルホラン、メチルスルホラン、アセトニトリル、クロロニトリル、プロピオニトリル、ホウ酸トリメチル、ケイ酸テトラメチル、ニトロメタン、ジメチルホルムアミド、N-メチルピロリドン、酢酸エチル、テトラヒドロチオフェン、ジメチルスルホキシド、3-メチル-2-オキサゾリドン、エチレングリコール、ジメチルサルファイト等の非プロトン性有機溶媒を用いることができる。
The non-aqueous electrolyte may be a liquid non-aqueous electrolyte or a polymer electrolyte such as a solid electrolyte or a gel electrolyte. In the former case, the non-aqueous electrolyte battery is configured as a so-called lithium ion battery, and in the latter case, the non-aqueous electrolyte battery is configured as a polymer electrolyte battery such as a polymer solid electrolyte battery or a polymer gel electrolyte battery.
In the case of a liquid nonaqueous electrolyte, the solvent is ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, 1,1- or 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltatrahydrofuran, γ-butyllactone, 1,3-dioxolane, 4-methyl-1,3-dioxolane, anisole, diethyl ether, sulfolane, methylsulfolane, acetonitrile, chloronitrile, propionitrile, trimethylborate Aprotic organic solvents such as tetramethyl silicate, nitromethane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, tetrahydrothiophene, dimethyl sulfoxide, 3-methyl-2-oxazolidone, ethylene glycol, dimethyl sulfite it can.
非水電解質を高分子固体電解質、高分子電解質などの高分子電解質とする場合には、可塑剤（非水電解液）でゲル化されたマトリクス高分子化合物を含むが、このマトリクス高分子化合物としては、ポリエチレンオキサイドやその架橋体などのエーテル系高分子化合物、ポリメタクリレート系高分子化合物、ポリアクリレート系高分子化合物、ポリビニリデンフルオライドやビニリデンフルオライド−ヘキサフルオロプロピレン共重合体などのフッ素系高分子化合物などを単独、もしくは混合して用いることができる。
これらの中で、酸化還元安定性の観点などから、ポリビニリデンフルオライドやビニリデンフルオライド−ヘキサフルオロプロピレン共重合体などのフッ素系高分子化合物を用いることが好ましい。
When the nonaqueous electrolyte is a polymer electrolyte such as a polymer solid electrolyte or a polymer electrolyte, the matrix polymer compound gelled with a plasticizer (nonaqueous electrolyte) is included. Fluorine polymers such as ether polymer compounds such as polyethylene oxide and cross-linked polymers thereof, polymethacrylate polymer compounds, polyacrylate polymer compounds, polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymers. Molecular compounds can be used alone or in combination.
Among these, it is preferable to use a fluorine-based polymer compound such as polyvinylidene fluoride or vinylidene fluoride-hexafluoropropylene copolymer from the viewpoint of redox stability.
これら高分子固体電解質、高分子ゲル電解質に含有される可塑剤を構成する電解質塩や非水系溶媒としては、前述のものがいずれも使用可能である。ゲル電解質の場合、可塑剤である非水電解液中の電解質塩濃度は、０．１〜５mol/Lが好ましく、０．５〜２．０mol/Lがより好ましい。 As the electrolyte salt and the non-aqueous solvent constituting the plasticizer contained in these polymer solid electrolyte and polymer gel electrolyte, any of those described above can be used. In the case of a gel electrolyte, the electrolyte salt concentration in the non-aqueous electrolyte that is a plasticizer is preferably 0.1 to 5 mol / L, and more preferably 0.5 to 2.0 mol / L.
このような固体電解質の作製方法としては特に制限はないが、例えば、マトリックスを形成する高分子化合物、リチウム塩および溶媒を混合し、加熱して溶融する方法、適当な混合用の有機溶媒に高分子化合物、リチウム塩および溶媒を溶解させた後、混合用の有機溶剤を蒸発させる方法、ならびにモノマー、リチウム塩および溶媒を混合し、それに紫外線、電子線または分子線などを照射してポリマーを形成させる方法などを挙げることができる。
また、前記固体電解質中の溶媒の添加割合は、１０〜９０質量％が好ましく、さらに好ましくは、３０〜８０質量％である。１０〜９０質量％であると、導電率が高く、かつ機械的強度が高く、フィルム化しやすい。
The method for producing such a solid electrolyte is not particularly limited. For example, a polymer compound that forms a matrix, a lithium salt, and a solvent are mixed, heated and melted, and an appropriate organic solvent for mixing is used. Method of evaporating the organic solvent for mixing after dissolving the molecular compound, lithium salt and solvent, and mixing the monomer, lithium salt and solvent, and irradiating them with ultraviolet rays, electron beams or molecular beams to form a polymer And the like.
Moreover, 10 to 90 mass% is preferable, and, as for the addition ratio of the solvent in the said solid electrolyte, More preferably, it is 30 to 80 mass%. When the content is 10 to 90% by mass, the electrical conductivity is high, the mechanical strength is high, and the film is easily formed.
本発明のリチウムイオン二次電池においては、セパレーターを使用することもできる。
セパレーターとしては、特に限定されるものではないが、例えば、織布、不織布、合成樹脂製微多孔膜などが挙げられる。特に合成樹脂製多孔膜が好適に用いられるが、その中でもポリオレフィン系微多孔膜が、厚さ、膜強度、膜抵抗の面で好適である。具体的には、ポリエチレンおよびポリプロピレン製微多孔膜、またはこれらを複合した微多孔膜などである。
A separator can also be used in the lithium ion secondary battery of the present invention.
Although it does not specifically limit as a separator, For example, a woven fabric, a nonwoven fabric, a synthetic resin microporous film, etc. are mentioned. In particular, a synthetic resin porous membrane is preferably used. Among these, a polyolefin-based microporous membrane is preferable in terms of thickness, membrane strength, and membrane resistance. Specifically, it is a microporous film made of polyethylene and polypropylene, or a microporous film in which these are combined.
本発明のリチウムイオン二次電池においては、初期充放電効率が高いことから、ゲル電解質を用いることも可能である。
ゲル電解質二次電池は、炭素材料を含有する負極と、正極およびゲル電解質を、例えば、負極、ゲル電解質、正極の順で積層し、電池外装材内に収容することで構成される。なお、これに加えてさらに負極と正極の外側にゲル電解質を配するようにしてもよい。このような炭素材料を負極に用いるゲル電解質二次電池では、ゲル電解質にプロピレンカーボネートが含有され、また炭素材料粉末としてインピーダンスを十分に低くできる程度に小粒径のものを用いた場合でも、不可逆容量が小さく抑えられる。したがって、大きな放電容量が得られるとともに高い初期充放電効率が得られる。
In the lithium ion secondary battery of the present invention, a gel electrolyte can be used because of the high initial charge / discharge efficiency.
The gel electrolyte secondary battery is configured by laminating a negative electrode containing a carbon material, a positive electrode, and a gel electrolyte in the order of, for example, a negative electrode, a gel electrolyte, and a positive electrode, and accommodating them in a battery exterior material. In addition to this, a gel electrolyte may be further disposed outside the negative electrode and the positive electrode. In the gel electrolyte secondary battery using such a carbon material for the negative electrode, even when propylene carbonate is contained in the gel electrolyte and the carbon material powder has a particle size small enough to reduce the impedance sufficiently, it is irreversible. Capacity is kept small. Therefore, a large discharge capacity is obtained and a high initial charge / discharge efficiency is obtained.
さらに、本発明に係るリチウムイオン二次電池の構造は任意であり、その形状、形態について特に限定されるものではなく、円筒型、角型、コイン型、ボタン型などの中から任意に選択することができる。より安全性の高い密閉型非水電解液電池を得るためには、過充電などの異常時に電池内圧上昇を感知して電流を遮断させる手段を備えたものであることが好ましい。高分子固体電解質電池や高分子ゲル電解質電池の場合には、ラミネートフィルムに封入した構造とすることもできる。 Further, the structure of the lithium ion secondary battery according to the present invention is arbitrary, and the shape and form thereof are not particularly limited, and are arbitrarily selected from a cylindrical shape, a square shape, a coin shape, a button shape, and the like. be able to. In order to obtain a sealed nonaqueous electrolyte battery with higher safety, it is preferable to include a means for detecting an increase in the internal pressure of the battery and shutting off the current when there is an abnormality such as overcharging. In the case of a polymer solid electrolyte battery or a polymer gel electrolyte battery, a structure enclosed in a laminate film can also be used.
次に本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。また以下の実施例および比較例では、炭素材料を図1に示すような構成の評価用ボタン型二次電池を作製して評価したが、実電池は、本発明の概念に基づき、公知の方法に準じて作製することができる。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Further, in the following examples and comparative examples, the carbon material was evaluated by producing a button-type secondary battery for evaluation having a configuration as shown in FIG. 1, but the actual battery is a known method based on the concept of the present invention. It can produce according to.
（実施例1）
鉄を４．０質量％および珪素を０．３質量％含有する直径１００〜３００ｎｍおよび長さが２〜２０μｍの炭素繊維を、平均粒径３２μｍのメソカーボン小球体の炭化物９５．５質量部に対して４．５質量部混合した。なお、用いたメソカーボン小球体炭化物は高温熱処理したときに黒鉛化が促進される易黒鉛化性炭素材料であるコールタールピッチから製造されるものを３００〜５００℃で焼成したものである。この混合物１００ｇに対しタール軽油を２００ｍＬ滴下し、超音波洗浄器を用いて２０分間分散させた。その後、メンブランフィルターを設置した吸引ろ過器を用いてタール中油と混合物とを分離した。得られた混合物を、真空乾燥機を用いて６０℃で２時間乾燥した。原料の組成を表１に示した。
乾燥した混合物を黒鉛るつぼに充填し、タンマン炉を用いて２８００℃で５時間高温処理して、炭素材料を得た。該炭素材料の結晶性を知るためにＸ線回折による格子面間隔ｄ００２を測定した。
(Example 1)
Carbon fiber having a diameter of 100 to 300 nm and a length of 2 to 20 μm containing 4.0% by mass of iron and 0.3% by mass of silicon was added to 95.5 parts by mass of carbide of mesocarbon microspheres having an average particle size of 32 μm. In contrast, 4.5 parts by mass were mixed. In addition, the mesocarbon microsphere carbide used is one obtained by calcining at 300 to 500 ° C. that is manufactured from coal tar pitch, which is a graphitizable carbon material whose graphitization is promoted when subjected to high-temperature heat treatment. 200 mL of tar light oil was added dropwise to 100 g of this mixture and dispersed for 20 minutes using an ultrasonic cleaner. Thereafter, the tar oil and the mixture were separated using a suction filter provided with a membrane filter. The obtained mixture was dried at 60 ° C. for 2 hours using a vacuum dryer. Table 1 shows the composition of the raw materials.
The dried mixture was filled in a graphite crucible and subjected to high temperature treatment at 2800 ° C. for 5 hours using a Tamman furnace to obtain a carbon material. In order to know the crystallinity of the carbon material, the lattice spacing d 002 by X-ray diffraction was measured.
なお、平均粒径はレーザー回折式粒度分布計により測定した粒度分布の累積度数が体積百分率で５０％となる粒子径とした。
Ｘ線回折による格子面間隔ｄ００２は、Ｘ線としてＣｕＫα線を用い、高純度シリコンを標準物質に使用して炭素材料の（００２）回折ピークを測定し、そのピークの位置より算出する。算出方法は、学振法（日本学術振興会第１７委員会が定めた測定法）に従うものであり、具体的には、「炭素繊維」（大谷杉郎、７３３−７４２頁（１９８６年）、近代編集社）などに記載された方法によって測定した値である。
真密度はＪＩＳ Ｒ７２２２−１９９７の６．真比重の測定方法により求めた。
The average particle size was a particle size at which the cumulative frequency of the particle size distribution measured by a laser diffraction particle size distribution meter was 50% by volume.
The lattice spacing d 002 by X-ray diffraction is calculated from the position of the peak by measuring the (002) diffraction peak of the carbon material using CuKα ray as the X-ray and using high-purity silicon as the standard substance. The calculation method follows the Japan Science and Technology Act (measurement method defined by the 17th Committee of the Japan Society for the Promotion of Science). Specifically, “Carbon Fiber” (Sugirou Otani, 733-742 (1986), It is a value measured by a method described in Modern Editorial Company).
The true density is JIS R7222-1997 6. It calculated | required with the measuring method of true specific gravity.
上記のようにして作製した炭素材料９０質量部と、結合剤としてのポリフッ化ビニリデン１０質量部とを、N−メチルピロリドンを溶媒として混合し、ホモミキサーを用いて５００rpmで５分間攪拌し、有機溶媒系負極合剤ペーストを調製した。
上記負極合剤ペーストを、銅箔（集電体7b）上に均一な厚さで塗布し、さらに真空中において９０℃で溶剤を揮発させて乾燥した。次に、この銅箔上に塗布された負極合剤をローラープレスによって加圧し、さらに直径１５．５ｍｍの円形状に打ち抜くことで、集電体に密着した負極合剤層からなる作用電極2を作製した。
90 parts by mass of the carbon material produced as described above and 10 parts by mass of polyvinylidene fluoride as a binder were mixed using N-methylpyrrolidone as a solvent, and stirred at 500 rpm for 5 minutes using a homomixer. A solvent-based negative electrode mixture paste was prepared.
The negative electrode mixture paste was applied on a copper foil (
対極4は、リチウム金属箔を、ニッケルネットに押付け、直系１５．５ｍｍの円形状に打ち抜いて、ニッケルネットからなる集電体（７a）と、当該集電体に密着したリチウム金属箔からなる対極4を作製した。
エチレンカーボネート３３質量部、メチルエチルカーボネート６７質量部の割合で混合してなる溶媒に、ＬｉＰＦ6を１mol/Lとなる濃度で溶解させ、非水電解液を調製した。得られた非水電解液をポリプロピレン多孔質体に含浸させ、電解質液が含浸されたセパレーター５を作製した。
The counter electrode 4 is formed by pressing a lithium metal foil against a nickel net and punching it into a direct 15.5 mm circular shape to form a current collector (7a) made of nickel net, and a counter electrode made of a lithium metal foil closely attached to the current collector. 4 was produced.
LiPF6 was dissolved at a concentration of 1 mol / L in a solvent prepared by mixing 33 parts by mass of ethylene carbonate and 67 parts by mass of methyl ethyl carbonate to prepare a nonaqueous electrolytic solution. The obtained non-aqueous electrolyte solution was impregnated into a polypropylene porous body to produce a separator 5 impregnated with the electrolyte solution.
評価電池として図1に示すボタン型二次電池を作製した。
評価電池は、外装カップ1と外装缶3とが、その周辺部において絶縁ガスケット6を介してかしめられた密閉構造を有し、その内部に、外装缶3の内面から順に、ニッケルネットからなる集電体７a、リチウム箔よりなる円盤状の作用電極2および銅箔からなる集電体7bが積層された電池系である。
評価電池とは、電解質溶液を含浸させたセパレーター5を、集電体7bに密着した作用電極2と、集電体7aに密着した対極4との間に挟んで積層した後、作用電極2を外装カップ1内に、対極4を外装缶3内に収容して、外装カップ1と外装缶3とを合わせ外装カップ1と外装缶3との周辺部を、絶縁ガスケット6を介してかしめ密閉して作製した。
この評価電池は、実電池において負極活物質として使用可能な黒鉛質粒子を含有する作用電極2と、リチウム金属箔からなる対極4とから構成される電池である。
A button-type secondary battery shown in FIG. 1 was produced as an evaluation battery.
The evaluation battery has a sealed structure in which the
The evaluation battery is formed by sandwiching the separator 5 impregnated with the electrolyte solution between the working
This evaluation battery is a battery including a working
上記のようにして作製された評価電池について、２５℃の温度下で下記のような充放電試験を行った。
０．９ｍＡの電流値で回路電圧が０ｍＶに達するまで定電流充電を行い、回路電圧が０ｍＶに達した時点で定電圧充電に切り替え、さらに電流値が２０μＡになるまで充電を続けた。その間の通電量から充電容量を求めた。その後、１２０分間休止した。
次に０．９ｍＡの電流値で、回路電圧が１．５Ｖに達するまで定電流充電を行い、その間の通電量から放電容量を求めた。この第1サイクルにおける通電量から充電容量と放電容量を求め、次式から不可逆容量と初期充放電効率を計算した。
不可逆容量＝充電容量−放電容量
初期充放電効率（％）＝（放電容量／充電容量）×１００
なお、この試験では、リチウムイオンを炭素材料中に吸蔵する過程を充電、炭素材料から脱離する過程を放電とした。
上記炭素材料の真密度（g/cm3)および格子面間隔ｄ００２（ｎｍ）と、上記炭素材料１ｇ当りの放電容量（mAh/g）、不可逆容量（mAh/g）および初期充放電効率（％）を表２に示した。
About the evaluation battery produced as mentioned above, the following charging / discharging tests were done at the temperature of 25 degreeC.
Constant current charging was performed until the circuit voltage reached 0 mV at a current value of 0.9 mA, and switching to constant voltage charging was performed when the circuit voltage reached 0 mV, and charging was continued until the current value reached 20 μA. The charging capacity was determined from the amount of electricity applied during that time. Then, it rested for 120 minutes.
Next, constant current charging was performed at a current value of 0.9 mA until the circuit voltage reached 1.5 V, and the discharge capacity was obtained from the energization during that time. The charge capacity and discharge capacity were determined from the energization amount in the first cycle, and the irreversible capacity and initial charge / discharge efficiency were calculated from the following equations.
Irreversible capacity = charge capacity-discharge capacity Initial charge / discharge efficiency (%) = (discharge capacity / charge capacity) × 100
In this test, the process of occluding lithium ions in the carbon material was charged, and the process of desorbing from the carbon material was discharge.
True density (g / cm 3 ) and lattice spacing d 002 (nm) of the carbon material, discharge capacity per 1 g of the carbon material (mAh / g), irreversible capacity (mAh / g), and initial charge / discharge efficiency ( %) Is shown in Table 2.
（実施例２）
実施例１において、メソカーボン小球体炭化物に添加する炭素繊維の代わりに、鉄を３．５質量％含有する直径１００〜３００ｎｍの未精製カーボンブラックを用いる以外は、実施例１と同様な方法と条件で、分散液の調製、ろ過分離、焼成、高温処理、負極合剤ペースト、作用電極の作製を行った。原料の組成は表１に示した。引続き、実施例１と同様に、評価電池の作製、充放電特性の試験を行った。その評価結果を表２に示した。
(Example 2)
In Example 1, instead of the carbon fiber added to the mesocarbon microsphere carbide, the same method as in Example 1 except that unrefined carbon black having a diameter of 100 to 300 nm containing 3.5% by mass of iron is used. Under the conditions, preparation of a dispersion, filtration separation, firing, high-temperature treatment, negative electrode mixture paste, and working electrode were performed. The composition of the raw materials is shown in Table 1. Subsequently, in the same manner as in Example 1, the evaluation battery was produced and the charge / discharge characteristics were tested. The evaluation results are shown in Table 2.
（実施例３）
実施例１において、メソカーボン小球体の炭化物に添加する炭素繊維４．５質量部の代わりに、珪素を５．５質量％含有する直径２〜５μｍの塊状人造黒鉛６．０質量部とメソカーボン小球体９４．０質量部を用いる以外は、実施例１と同様な方法と条件で、分散液の調製、ろ過分離、焼成、高温処理、負極合剤ペースト、作用電極の作製を行った。原料の組成は表１に示した。引続き、実施例１と同様に、評価電池の作製、充放電特性の試験を行った。その評価結果を表２に示した。
(Example 3)
In Example 1, instead of 4.5 parts by mass of carbon fiber added to the carbide of mesocarbon microspheres, 6.0 parts by mass of massive artificial graphite having a diameter of 2 to 5 μm containing 5.5% by mass of silicon and mesocarbon A dispersion was prepared, filtered and separated, baked, treated at high temperature, a negative electrode mixture paste, and a working electrode were prepared under the same method and conditions as in Example 1 except that 94.0 parts by mass of small spheres were used. The composition of the raw materials is shown in Table 1. Subsequently, in the same manner as in Example 1, the evaluation battery was produced and the charge / discharge characteristics were tested. The evaluation results are shown in Table 2.
（比較例1）
実施例１において、炭素繊維を用いることなく、実施例１と同様な方法と条件で、高温処理、負極合剤ペースト、作用電極の作製を行った。原料の組成は表１に示した。引続き、実施例１と同様に、評価電池の作製、充放電特性の試験を行った。その評価結果を表２に示した。
(Comparative Example 1)
In Example 1, a high-temperature treatment, a negative electrode mixture paste, and a working electrode were produced under the same method and conditions as in Example 1 without using carbon fiber. The composition of the raw materials is shown in Table 1. Subsequently, in the same manner as in Example 1, the evaluation battery was produced and the charge / discharge characteristics were tested. The evaluation results are shown in Table 2.
（比較例２）
実施例１において、メソカーボン小球体の炭化物に添加する炭素繊維の代わりに、鉄を３．８質量％含有する直径３〜６μｍの鱗片状天然黒鉛４．５質量部を用いる以外は、実施例１と同様な方法と条件で、分散液の調製、ろ過分離、焼成、高温処理、負極合剤ペースト、作用電極の作製を行った。原料の組成は表１に示した。引続き、実施例１と同様に、評価電池の作製、充放電特性の試験を行った。その評価結果を表２に示した。
(Comparative Example 2)
In Example 1, instead of the carbon fiber added to the carbide of mesocarbon microspheres, Example is used except that 4.5 parts by mass of scaly natural graphite having a diameter of 3 to 6 μm and containing 3.8% by mass of iron is used. Preparation of dispersion, filtration separation, firing, high-temperature treatment, negative electrode mixture paste, and working electrode were performed using the same method and conditions as in 1. The composition of the raw materials is shown in Table 1. Subsequently, in the same manner as in Example 1, the evaluation battery was produced and the charge / discharge characteristics were tested. The evaluation results are shown in Table 2.
（比較例３） 実施例１において、メソカーボン小球体の炭化物に添加する炭素繊維４．５質量部の代わりに、炭素繊維４０質量部を用いる以外は、実施例１と同様な方法と条件で、分散液の調製、ろ過分離、焼成、高温処理、負極合剤ペースト、作用電極の作製を行った。原料の組成は表１に示した。引続き、実施例１と同様に、評価電池の作製、充放電特性の試験を行った。その評価結果を表２に示した。 (Comparative example 3) In Example 1, it replaces with 4.5 mass parts of carbon fibers added to the carbide | carbonized_material of a mesocarbon microsphere, It is the same method and conditions as Example 1 except using 40 mass parts of carbon fibers. Preparation of dispersion, filtration separation, firing, high temperature treatment, negative electrode mixture paste, and working electrode were prepared. The composition of the raw materials is shown in Table 1. Subsequently, in the same manner as in Example 1, the evaluation battery was produced and the charge / discharge characteristics were tested. The evaluation results are shown in Table 2.
実施例1と比較例1とから、鉄および珪素を含む微小炭素繊維が、放電容量の向上に寄与したことが明確である。これは、鉄および珪素が、負極活物質の原料であるメソカーボン小球体の黒鉛化物との分散性が良好であることから、該黒鉛化物の結晶性向上作用した結果と推定される。また、実施例２および実施例３と比較例１とから、同様に、鉄または珪素を含む微小炭素の添加の放電容量への効果が明らかである。さらに微小炭素が鱗片状黒鉛であったり（比較例２）、微小炭素の配合量が３０質量％を超えて多い場合（比較例３）には、不可逆容量が大きく、初期充放電効率が劣る。特に、微小炭素の配合量が多いと、放電容量が低下する。 From Example 1 and Comparative Example 1, it is clear that the fine carbon fiber containing iron and silicon contributed to the improvement of the discharge capacity. This is presumed to be because iron and silicon have good dispersibility with the graphitized material of mesocarbon spherules, which are raw materials for the negative electrode active material, and thus the crystallinity of the graphitized material is improved. Further, from Examples 2 and 3 and Comparative Example 1, similarly, the effect on the discharge capacity of the addition of minute carbon containing iron or silicon is clear. Further, when the fine carbon is flaky graphite (Comparative Example 2) or the amount of the fine carbon is more than 30% by mass (Comparative Example 3), the irreversible capacity is large and the initial charge / discharge efficiency is inferior. In particular, when the amount of fine carbon is large, the discharge capacity decreases.
本発明にかかる炭素材料は、その特徴を活かして負極以外の用途に転用することもできるが、特に上記したリチウムイオン二次電池の負極として好適である。したがって本発明では、さらにこの炭素材料を用いたリチウムイオン二次電池負極、さらにはリチウムイオン二次電池が提供される。 Although the carbon material concerning this invention can also be diverted to uses other than a negative electrode taking advantage of the characteristic, it is suitable as a negative electrode of an above-described lithium ion secondary battery especially. Therefore, the present invention further provides a lithium ion secondary battery negative electrode and further a lithium ion secondary battery using this carbon material.
１ 外装カップ
２ 作用電極
３ 外装缶
４ 対極
５ 電解質溶液含浸セパレーター
６ 絶縁ガスケット
７a、７b 集電体
DESCRIPTION OF
Claims (6)
炭素繊維、カーボンナノチューブ、カーボンブラック、フラーレンまたは人造黒鉛である微小炭素、
ならびにメソカーボン小球体の炭化物を含み、
該微小炭素が該メソカーボン小球体の炭化物より小さく、
該元素の微小炭素に対する割合が０．１〜１０質量％であり、
該微小炭素の該メソカーボン小球体の炭化物に対する割合が０．０１〜３０質量％である組成物を、２０００℃以上で高温熱処理することを特徴とする炭素材料の製造方法。 At least one element selected from the group consisting of iron, cobalt, nickel, manganese, platinum, boron and silicon,
Carbon fiber, carbon nanotubes, carbon black, fullerene or artificial carbon, fine carbon,
As well as carbides of mesocarbon spherules ,
The microcarbon is smaller than the carbides of the mesocarbon spherules,
The ratio of the element to the minute carbon is 0.1 to 10% by mass,
The method of producing a carbon material, wherein the ratio carbides of the mesocarbon spherules of the fine carbon composition is 0.01 to 30 wt%, a high temperature heat treatment at 2000 ° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004102892A JP4628007B2 (en) | 2004-03-31 | 2004-03-31 | Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004102892A JP4628007B2 (en) | 2004-03-31 | 2004-03-31 | Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005289661A JP2005289661A (en) | 2005-10-20 |
| JP2005289661A5 JP2005289661A5 (en) | 2007-05-24 |
| JP4628007B2 true JP4628007B2 (en) | 2011-02-09 |
Family
ID=35323049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004102892A Expired - Lifetime JP4628007B2 (en) | 2004-03-31 | 2004-03-31 | Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4628007B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100830612B1 (en) | 2006-05-23 | 2008-05-21 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05330915A (en) * | 1992-05-26 | 1993-12-14 | Yazaki Corp | Production of carbon/carbon composite material |
| JP2002146635A (en) * | 2000-11-06 | 2002-05-22 | Petoca Ltd | Highly graphiteized carbon material, method for producing the same, and application thereof |
-
2004
- 2004-03-31 JP JP2004102892A patent/JP4628007B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05330915A (en) * | 1992-05-26 | 1993-12-14 | Yazaki Corp | Production of carbon/carbon composite material |
| JP2002146635A (en) * | 2000-11-06 | 2002-05-22 | Petoca Ltd | Highly graphiteized carbon material, method for producing the same, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005289661A (en) | 2005-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7892677B2 (en) | Negative electrode for non-aqueous electrolyte secondary batteries, and non-aqueous electrolyte secondary battery having the same | |
| JP3995050B2 (en) | Composite particles for negative electrode material of lithium ion secondary battery and method for producing the same, negative electrode material and negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP3285520B2 (en) | Graphite particles, method for producing graphite particles, graphite paste using graphite particles, negative electrode for lithium secondary battery, and lithium secondary battery | |
| JP6316466B2 (en) | Carbonaceous coated graphite particles, production method thereof, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP4792618B2 (en) | Carbonaceous particles for negative electrode of lithium secondary battery, manufacturing method thereof, negative electrode of lithium secondary battery and lithium secondary battery | |
| JP4689391B2 (en) | Method for producing graphite material for negative electrode material of lithium ion secondary battery | |
| JP2011243567A (en) | Negative electrode material for lithium ion secondary battery and method of manufacturing the same, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP3213575B2 (en) | Negative electrode for lithium secondary battery, method for producing the same, and lithium secondary battery | |
| JP4354723B2 (en) | Method for producing graphite particles | |
| JP2016122516A (en) | Negative electrode material for lithium ion secondary battery and manufacturing method thereof, negative electrode for lithium ion secondary battery arranged by use thereof, and lithium ion secondary battery | |
| JP4996827B2 (en) | Metal-graphite composite particles for negative electrode of lithium ion secondary battery and manufacturing method thereof, negative electrode material and negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| CN112424118A (en) | Method for producing monolithic mesophase graphitized article | |
| JP5133543B2 (en) | Method for producing mesocarbon microsphere graphitized material | |
| JP3732654B2 (en) | Graphite particles, negative electrode for lithium secondary battery, and lithium secondary battery | |
| JPH11217266A (en) | Graphite particle, its production and negative electrode for lithium secondary battery and lithium secondary battery | |
| JP5066132B2 (en) | Polycrystalline mesocarbon microsphere graphitized product, negative electrode active material, and lithium ion secondary battery | |
| JP4643165B2 (en) | Carbon material, negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery | |
| JP3951219B2 (en) | Negative electrode for lithium secondary battery, method for producing the same, and lithium secondary battery | |
| JP4628007B2 (en) | Carbon material manufacturing method, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP4335596B2 (en) | Method for producing polycrystalline mesocarbon microsphere graphitized product | |
| JP5865273B2 (en) | Method for producing graphite material | |
| JPH10236808A (en) | Graphite grain, its production, graphite paste using graphite grain, negative electrode for lithium secondary battery, its production and lithium secondary battery | |
| JP5001977B2 (en) | Graphite particles, lithium ion secondary battery and negative electrode material thereof | |
| JP4135162B2 (en) | Negative electrode for lithium secondary battery | |
| JP3325021B2 (en) | Graphite particles for negative electrode of lithium secondary battery and graphite paste for negative electrode of lithium secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070323 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070329 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100723 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100727 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100924 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101102 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101109 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131119 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4628007 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |