JPWO2014115322A1 - Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using them - Google Patents
Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using them Download PDFInfo
- Publication number
- JPWO2014115322A1 JPWO2014115322A1 JP2014558401A JP2014558401A JPWO2014115322A1 JP WO2014115322 A1 JPWO2014115322 A1 JP WO2014115322A1 JP 2014558401 A JP2014558401 A JP 2014558401A JP 2014558401 A JP2014558401 A JP 2014558401A JP WO2014115322 A1 JPWO2014115322 A1 JP WO2014115322A1
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- active material
- lithium ion
- ion secondary
- electrode active
- 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.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000011162 core material Substances 0.000 claims abstract description 11
- 238000005259 measurement Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 4
- 230000006866 deterioration Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 description 34
- 229910002804 graphite Inorganic materials 0.000 description 29
- 239000010439 graphite Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000003792 electrolyte Substances 0.000 description 15
- -1 alkali metal salt Chemical class 0.000 description 13
- 239000003575 carbonaceous material Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000011362 coarse particle Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Chemical class 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-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
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-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
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- AETJTBDBQRMLLQ-UHFFFAOYSA-N 4-chloro-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Cl AETJTBDBQRMLLQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- IZJSTXINDUKPRP-UHFFFAOYSA-N aluminum lead Chemical compound [Al].[Pb] IZJSTXINDUKPRP-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical group FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/621—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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
リチウムイオンを吸蔵・放出するリチウムイオン二次電池用負極活物質であって、前記負極活物質は、炭素よりなる核材を有し、密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・ｃｍ以上で、かつ式（１）を満たし、前記炭素は、Ｘ線回折装置測定により求められる炭素００２面の面間隔が０．３３４ｎｍ以上０．３３８ｎｍ以下であることを特徴とする。式（１）： ｒ2≧０．１３× ｒ1式（１）において、ｒ2は、密度２．０ｇ／ｃｃにおける体積抵抗率、ｒ1は、密度１．２ｇ／ｃｃにおける体積抵抗率を表す。本発明の負極活物質を用いることにより、信頼性を向上させたリチウムイオン二次電池を提供すること可能となる。特に、サイクル劣化時における大電流を抑制することができる。A negative electrode active material for lithium ion secondary batteries that occludes / releases lithium ions, the negative electrode active material having a core material made of carbon and having a volume resistivity of 0.32Ω at a density of 2.0 g / cc. The distance between the carbon 002 planes determined by X-ray diffractometer measurement is 0.334 nm or more and 0.338 nm or less. Formula (1): r2 ≧ 0.13 × r1 In formula (1), r2 represents a volume resistivity at a density of 2.0 g / cc, and r1 represents a volume resistivity at a density of 1.2 g / cc. By using the negative electrode active material of the present invention, a lithium ion secondary battery with improved reliability can be provided. In particular, a large current during cycle deterioration can be suppressed.
Description
本発明は、リチウムイオン二次電池用負極活物質及びそれらを用いたリチウムイオン二次電池に関する。 The present invention relates to a negative electrode active material for a lithium ion secondary battery and a lithium ion secondary battery using them.
近年、リチウムイオン二次電池に対する開発が盛んに進められている。１９８０年代，１９９０年代の携帯電話やノートＰＣの発達に伴い、それらの電源用として二次電池は高性能化されている。二次電池としては鉛蓄電池やニッカド電池より、高エネルギー密度を持つリチウムイオン二次電池が主に用いられている。 In recent years, development of lithium ion secondary batteries has been actively promoted. With the development of mobile phones and notebook PCs in the 1980s and 1990s, secondary batteries have been improved in performance as power sources for them. As the secondary battery, a lithium ion secondary battery having a higher energy density is mainly used than a lead storage battery or a nickel cadmium battery.
負極活物質としてリチウムイオンの吸蔵・放出が可能な炭素材料を用いた場合、充電時に、炭素材料の層間にリチウムイオンが吸蔵されるため、負極上に金属リチウムが析出することがなく、デンドライトによる内部短絡の問題を回避することができる。しかしながら、負極材料として炭素材料を用いた電池においても、電池内で正極と負極とが接触し、内部短絡が発生することがある。内部短絡が発生すると、正極と負極とが接触した部分に大電流が集中するとともに発熱が起こり、電池の温度が急激に上昇して発火に至る可能性がある。 When a carbon material capable of occluding and releasing lithium ions is used as the negative electrode active material, lithium ions are occluded between the layers of the carbon material during charging. The problem of internal short circuit can be avoided. However, even in a battery using a carbon material as a negative electrode material, the positive electrode and the negative electrode may be in contact with each other in the battery and an internal short circuit may occur. When an internal short circuit occurs, a large current is concentrated at a portion where the positive electrode and the negative electrode are in contact with each other, and heat is generated, which may cause the battery temperature to rise rapidly and lead to ignition.
また、リチウムイオン二次電池の電解液には、主に非水溶媒が用いられている。従って、過充電，加熱，短絡などが生じても発熱暴走状態となったりせず、さらに、電池が破裂発火しないよう信頼性の確保が重要である。 Moreover, a nonaqueous solvent is mainly used for the electrolyte solution of the lithium ion secondary battery. Therefore, it is important to ensure reliability so that the battery does not run out of heat even if overcharge, heating, short circuit, etc. occur, and the battery does not burst and ignite.
信頼性を高めるための技術として、特開２００４−３９５５８号公報（特許文献１）では、正負極に、１８０℃における体積抵抗率が−２０℃以上〜６０℃における体積抵抗率に比べて２.５倍以上である導電材を設けることが開示されている。その結果、短絡電流による急激な温度上昇を抑制することができる。 As a technique for improving the reliability, in Japanese Patent Application Laid-Open No. 2004-39558 (Patent Document 1), the positive and negative electrodes have a volume resistivity at 180 ° C. of −20 ° C. or more to 60 ° C. compared with the volume resistivity of 2. It is disclosed to provide a conductive material that is five times or more. As a result, a rapid temperature increase due to a short-circuit current can be suppressed.
さらに、特開２０１１−７６８２２号公報（特許文献２）には、負極活物質層の体積抵抗率を上昇させることが開示されている。 Furthermore, JP 2011-76822 A (Patent Document 2) discloses increasing the volume resistivity of the negative electrode active material layer.
特許文献１のように、高温にならないと短絡電流が抑えられないシャットダウン機構には、常温での発熱を穏やかにする効果がない。従って、１００〜２００℃以下で電流を流れにくくすることができても、急激な発熱では、正極や負極や電解液がそれまでに自己発熱する温度に達してしまうと、継続的に発熱が起こり、熱暴走してしまうおそれがある。
As in
特許文献２のように、体積抵抗率を単純に増大させる場合、サイクル劣化後の信頼性向上への寄与が小さい。また、電池の抵抗を増大させてしまうおそれがある。 When the volume resistivity is simply increased as in Patent Document 2, the contribution to improving reliability after cycle deterioration is small. Moreover, there exists a possibility of increasing the resistance of a battery.
従って本発明の目的は、電池の抵抗の上昇を抑制しつつ、リチウムイオン二次電池の信頼性を向上させることにある。 Accordingly, an object of the present invention is to improve the reliability of a lithium ion secondary battery while suppressing an increase in battery resistance.
上記課題を解決するための本発明の特徴は以下の通りである。リチウムイオンを吸蔵・放出するリチウムイオン二次電池用負極活物質であって、前記負極活物質は、炭素よりなる核材を有し、密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・ｃｍ以上で、かつ式（１）を満たし、前記炭素は、Ｘ線回折装置測定により求められる炭素００２面の面間隔が０．３３４ｎｍ以上０．３３８ｎｍ以下であることを特徴とするリチウムイオン二次電池負極活物質。
式（１）： ｒ2≧０．１３× ｒ1
式（１）において、ｒ2は、密度２．０ｇ／ｃｃにおける体積抵抗率、ｒ1は、密度１．２ｇ／ｃｃにおける体積抵抗率を表す。The features of the present invention for solving the above-described problems are as follows. A negative electrode active material for lithium ion secondary batteries that occludes / releases lithium ions, the negative electrode active material having a core material made of carbon and having a volume resistivity of 0.32Ω at a density of 2.0 g / cc. Lithium ion dioxide characterized in that it is cm or more and satisfies the formula (1), and the carbon has a plane spacing of the carbon 002 plane determined by X-ray diffractometer measurement of 0.334 nm or more and 0.338 nm or less. Secondary battery negative electrode active material.
Formula (1): r 2 ≧ 0.13 × r 1
In formula (1), r 2 represents the volume resistivity at a density of 2.0 g / cc, and r 1 represents the volume resistivity at a density of 1.2 g / cc.
本発明によると、電池の抵抗の上昇を抑制しつつ、リチウムイオン二次電池の信頼性を向上させたリチウムイオン二次電池用負極活物質を提供することができる。特に、サイクル劣化後の電池での効果が大きい。上記した以外の課題、構成及び効果は以下の実施形態の説明により明らかにされる。 ADVANTAGE OF THE INVENTION According to this invention, the negative electrode active material for lithium ion secondary batteries which improved the reliability of the lithium ion secondary battery can be provided, suppressing the raise of resistance of a battery. In particular, the effect of the battery after cycle deterioration is great. Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.
以下、図面等を用いて、本発明の実施形態について説明する。以下の説明は本発明の内容の具体例を示すものであり、本発明がこれらの説明に限定されるものではなく、本明細書に開示される技術的思想の範囲内において当業者による様々な変更および修正が可能である。また、本発明を説明するための全図において、同一の機能を有するものは、同一の符号を付け、その繰り返しの説明は省略する場合がある。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. The following description shows specific examples of the contents of the present invention, and the present invention is not limited to these descriptions. Various modifications by those skilled in the art are within the scope of the technical idea disclosed in this specification. Changes and modifications are possible. In all the drawings for explaining the present invention, components having the same function are denoted by the same reference numerals, and repeated description thereof may be omitted.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。また、本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書で引用した全ての刊行物、特許及び特許出願をそのまま参考として本明細書に取り入れるものとする。 In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.
図１は、本発明の一実施形態に係る電池の内部構造を模式的に表す図である。図１に示す本発明の一実施形態に係る電池１は、正極１０、セパレータ１１、負極１２、電池缶１３、正極集電タブ１４、負極集電タブ１５、内蓋１６、内圧開放弁１７、ガスケット１８、正温度係数（Ｐｏｓｉｔｉｖｅ ｔｅｍｐｅｒａｔｕｒｅ ｃｏｅｆｆｉｃｉｅｎｔ；ＰＴＣ）抵抗素子１９、及び電池蓋２０、軸心２１から構成される。電池蓋２０は、内蓋１６、内圧開放弁１７、ガスケット１８、及び抵抗素子１９からなる一体化部品である。また、軸心２１には、正極１０、セパレータ１１及び負極１２が捲回されている。
FIG. 1 is a diagram schematically showing the internal structure of a battery according to an embodiment of the present invention. A
セパレータ１１を正極１０及び負極１２の間に挿入し、軸心２１に捲回した電極群を作製する。軸心２１は、正極１０、セパレータ１１及び負極１２を担持できるものであれば、公知の任意のものを用いることができる。電極群は、図１に示した円筒形状の他に、短冊状電極を積層したもの、又は正極１０と負極１２を扁平状等の任意の形状に捲回したもの等、種々の形状にすることができる。電池缶１３の形状は、電極群の形状に合わせ、円筒形、偏平長円形状、扁平楕円形状、角形等の形状を選択してもよい。
The
電池缶１３の材質は、アルミニウム、ステンレス鋼、ニッケルメッキ鋼製等、非水電解質に対し耐食性のある材料から選択される。また、電池缶１３を正極１０又は負極１２に電気的に接続する場合は、非水電解質と接触している部分において、電池缶１３の腐食やリチウムイオンとの合金化による材料の変質が起こらないように、電池容器１３の材料の選定を行う。
The material of the battery can 13 is selected from materials that are corrosion resistant to the non-aqueous electrolyte, such as aluminum, stainless steel, and nickel-plated steel. Further, when the battery can 13 is electrically connected to the
電池缶１３に電極群を収納し、電池缶１３の内壁に負極集電タブ１５を接続し、電池蓋２０の底面に正極集電タブ１４を接続する。電解液は、電池の密閉の前に電池缶１３の内部に注入する。電解液の注入方法は、電池蓋２０を解放した状態にて電極群に直接添加する方法、又は電池蓋２０に設置した注入口から添加する方法がある。
The electrode group is housed in the battery can 13, the negative electrode
その後、電池蓋２０を電池缶１３に密着させ、電池全体を密閉する。電解液の注入口がある場合は、それも密封する。電池を密閉する方法には、溶接、かしめ等公知の技術がある。
Thereafter, the
本発明の一実施形態に係るリチウムイオン二次電池は、例えば、下記のような負極と正極とをセパレータを介して対向して配置し、電解質を注入することによって製造することができる。本発明の一実施形態に係るリチウムイオン二次電池の構造は特に限定されないが、通常、正極及び負極とそれらを隔てるセパレータとを捲回して捲回式電極群にするか、又は正極、負極及びセパレータを積層させて積層型の電極群とすることができる。 The lithium ion secondary battery according to an embodiment of the present invention can be manufactured by, for example, disposing the following negative electrode and positive electrode facing each other via a separator and injecting an electrolyte. The structure of the lithium ion secondary battery according to one embodiment of the present invention is not particularly limited. Usually, the positive electrode and the negative electrode and the separator separating them are wound into a wound electrode group, or the positive electrode, the negative electrode, and the negative electrode A separator can be laminated to form a laminated electrode group.
図１に示す電池の構成は、本発明の一実施形態に係るリチウムイオン二次電池用負極活物質を適用可能なリチウムイオン二次電池の内部構造のあくまでも一例であり、本発明の一実施形態に係る負極が適用可能な電池は図１に記載のものに制限されるものでない。 The configuration of the battery shown in FIG. 1 is merely an example of the internal structure of a lithium ion secondary battery to which the negative electrode active material for a lithium ion secondary battery according to an embodiment of the present invention can be applied. The battery to which the negative electrode according to the invention is applicable is not limited to that shown in FIG.
＜負極＞
前記の問題に鑑み、発明者らが鋭意検討を行った結果、サイクル劣化後のリチウムイオン二次電池の信頼性には、高密度時の体積抵抗率が大きい負極活物質を用いる事が重要である事がわかった。負極活物質として黒鉛を用いた場合、サイクル劣化後の負極は、負極中の黒鉛が膨張収縮により移動することで、負極内に黒鉛粒子の分布が生まれ、黒鉛が疎な部分と密な部分が存在する。そして、内部短絡が発生した際に黒鉛が密な部分で大電流が流れると推測される。この黒鉛が密な負極部分で流れる常温での電流を抑制することが、内部短絡が発生した際の発火を防ぐ点において、重要であることを見出した。黒鉛が高密度になった箇所は、低密度の箇所に比べて電子伝導性が高く、大電流が流れてしまうため、高密度時の体積抵抗率の大きな黒鉛を用いることが重要である。<Negative electrode>
In view of the above problems, as a result of intensive studies by the inventors, it is important to use a negative electrode active material having a large volume resistivity at high density for the reliability of a lithium ion secondary battery after cycle deterioration. I knew that there was. When graphite is used as the negative electrode active material, the negative electrode after cycle deterioration has a distribution of graphite particles in the negative electrode due to the movement of graphite in the negative electrode due to expansion and contraction. Exists. And when an internal short circuit generate | occur | produces, it is estimated that a heavy current flows in a graphite dense part. It has been found that it is important to suppress the current at room temperature through which the graphite flows in a dense negative electrode portion in order to prevent ignition when an internal short circuit occurs. A portion where the graphite has a high density has higher electron conductivity than a low density portion, and a large current flows. Therefore, it is important to use a graphite having a large volume resistivity at a high density.
一方で、サイクル劣化後の黒鉛が高密度な状態に比べて、黒鉛が低密度な状態での体積抵抗率は大きくないことが好ましい。低密度での体積抵抗率が大きい場合、電子伝導性が低下し、電池の抵抗が大きくなってしまうからである。また、サイクル劣化後の電流は高密度領域で流れるため、リチウムイオン二次電池の信頼性の向上への効果も小さい。 On the other hand, it is preferable that the volume resistivity in a low-density state of graphite is not large as compared with a high-density state of graphite after cycle deterioration. This is because when the volume resistivity at a low density is large, the electron conductivity is lowered and the resistance of the battery is increased. In addition, since the current after cycle deterioration flows in a high density region, the effect of improving the reliability of the lithium ion secondary battery is small.
すなわち、低密度から高密度に変化した際の体積抵抗率の減少量が小さい負極活物質を用いる事で、初期の抵抗が小さくサイクル劣化後の電池の信頼性向上を両立出来ることを見出した。 That is, it has been found that by using a negative electrode active material having a small decrease in volume resistivity when changing from a low density to a high density, the initial resistance is small and the reliability of the battery after cycle deterioration can be improved.
本発明の負極活物質は、ＸＲＤ測定により求められる炭素００２面の面間隔が０．３３４ｎｍ〜０．３３８ｎｍの炭素材料であって、密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・cm以上でかつ以下式（１）を満たす事を特徴としたリチウムイオン二次電池負極用炭素粒子である。
式（１） ｒ2≧０．１３× ｒ1
ｒ1は、密度１．２ｇ／ｃｃの体積抵抗率
ｒ2は、密度２．０ｇ／ｃｃの体積抵抗率The negative electrode active material of the present invention is a carbon material having a carbon 002 plane spacing of 0.334 nm to 0.338 nm determined by XRD measurement, and has a volume resistivity of 0.32 Ω · cc at a density of 2.0 g / cc. It is carbon particle for lithium ion secondary battery negative electrodes characterized by satisfy | filling following formula (1) more than cm.
Formula (1) r 2 ≧ 0.13 × r 1
r 1 is the volume resistivity with a density of 1.2 g / cc.
r 2 is the volume resistivity with a density of 2.0 g / cc.
密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・ｃｍ未満の場合、サイクル劣化後のリチウムイオン二次電池の信頼性が低下するおそれがある。２．０ｇ／ｃｃの体積抵抗率は０．３３Ω・ｃｍ以上が好ましく、さらに０．３４Ω・ｃｍ以上が好ましい。 When the volume resistivity at a density of 2.0 g / cc is less than 0.32 Ω · cm, the reliability of the lithium ion secondary battery after cycle deterioration may be lowered. The volume resistivity of 2.0 g / cc is preferably 0.33 Ω · cm or more, more preferably 0.34 Ω · cm or more.
またｒ2＜０．１３× ｒ1の場合、電池の初期の抵抗が増大してしまうため、好ましくない。ｒ2≧０．１３× ｒ1を満たすこと好ましく、ｒ2≧０．１４× ｒ1を満たす方がさらに好ましい。Further, when r 2 <0.13 × r 1 , the initial resistance of the battery increases, which is not preferable. It is preferable to satisfy r 2 ≧ 0.13 × r 1, and it is more preferable that r 2 ≧ 0.14 × r 1 is satisfied.
負極の体積抵抗率を増大させる手段の例として、炭素活物質表面に酸化物や窒化物等の無機物や、ポリマー等で吸着もしくは被覆する方法が挙げられる。なお、本発明の吸着は物理吸着を表す。 Examples of means for increasing the volume resistivity of the negative electrode include a method in which the surface of the carbon active material is adsorbed or coated with an inorganic material such as an oxide or nitride, a polymer, or the like. The adsorption according to the present invention represents physical adsorption.
吸着、被覆させる材料は、黒鉛表面になるべく均一、平滑で存在出来る事が好ましい。不均一な場合、低密度から高密度へ変化した際の体積抵抗率の減少が大きい傾向がある。 The material to be adsorbed and coated should preferably be as uniform and smooth as possible on the graphite surface. In the case of non-uniformity, the volume resistivity tends to decrease greatly when changing from a low density to a high density.
また、吸着、被覆させる材料は、高密度時に変形、切断、崩壊が起こりにくい材料が好ましい。特に切断、崩壊が起こった場合、低密度から高密度へ変化した際の体積抵抗率の減少が大きい傾向がある。 Further, the material to be adsorbed and coated is preferably a material that hardly deforms, cuts or collapses at high density. In particular, when cutting or collapsing occurs, the volume resistivity tends to decrease greatly when changing from low density to high density.
酸化物で被覆する場合、材料はリチウムイオンと合金化しない材料が好ましい。リチウムイオンと合金化する材料は、合金化することで膨張しやすく、このような材料を用いた場合サイクル特性が悪化する場合がある。 When coating with an oxide, the material is preferably a material that does not alloy with lithium ions. A material that is alloyed with lithium ions easily expands when alloyed, and when such a material is used, the cycle characteristics may deteriorate.
吸着、被覆させる材料は、窒化物や、酸化物やポリマーの中では特にポリマーが好ましい。ポリマーの場合、無機物や、酸化物に比べて比較的安価でかつ平滑に吸着させやすいためである。 As the material to be adsorbed and coated, a polymer is particularly preferable among nitrides, oxides and polymers. This is because a polymer is relatively inexpensive and easily adsorbed smoothly compared to an inorganic substance or an oxide.
ポリマーとして具体的には、ポリビニルスルホン酸、ポリビニルスルホン酸Ｎａ、ポリスチレンスルホン酸、ポリスチレンスルホン酸Ｎａ、ポリアクリル酸，ポリアクリル酸塩，ポリアクリル酸エステル，ポリメタクリル酸，ポリメタクリル酸塩，ポリメタクリル酸エステル等が挙げられる。ポリマーの重量平均分子量は、１万〜１２０万であることが望ましい。上記の重量平均分子量は、液体クロマトグラフィーにより測定した値とする。 Specific examples of the polymer include polyvinyl sulfonic acid, polyvinyl sulfonic acid Na, polystyrene sulfonic acid, polystyrene sulfonic acid Na, polyacrylic acid, polyacrylic acid salt, polyacrylic acid ester, polymethacrylic acid, polymethacrylic acid salt, polymethacrylic acid salt. Acid ester etc. are mentioned. The weight average molecular weight of the polymer is desirably 10,000 to 1,200,000. The weight average molecular weight is a value measured by liquid chromatography.
溶解性の観点から、ポリマーは、重合性官能基としてビニル基、スチレン基を有するモノマーの重合体であることが望ましい。 From the viewpoint of solubility, the polymer is preferably a polymer of a monomer having a vinyl group or a styrene group as a polymerizable functional group.
また、極性の観点からは、ポリマーは、ビニル基よりもスチレン基のような芳香族化合物を持つモノマーの重合体であることが好ましい。極性を高くすることで、吸着均一性が向上するためである。 From the viewpoint of polarity, the polymer is preferably a polymer of a monomer having an aromatic compound such as a styrene group rather than a vinyl group. This is because the adsorption uniformity is improved by increasing the polarity.
ポリマーは、硫黄含有官能基を有することが特に好ましい。硫黄含有官能基としては、例えば、スルホン酸基、スルホン酸塩基、スルホニル基、チオール基、スルフィド基等が挙げられる。これらの官能基は極性が高く、吸着均一性が向上するためである。硫黄含有官能基として、これらの官能基を一種単独または複数種用いても良い。吸着均一性が向上することによって、低密度から高密度へ変化した際の体積抵抗率の減少が小さくなる。 It is particularly preferred that the polymer has a sulfur-containing functional group. Examples of the sulfur-containing functional group include a sulfonic acid group, a sulfonic acid group, a sulfonyl group, a thiol group, and a sulfide group. This is because these functional groups are highly polar and the adsorption uniformity is improved. One or more of these functional groups may be used as the sulfur-containing functional group. By improving the adsorption uniformity, the decrease in volume resistivity when changing from low density to high density is reduced.
また、ｐＨの観点では特に官能基を塩にしている物が好ましい。例えば、アルカリ金属塩であり、カウンターイオンとしてはＬｉ，Ｎａ，Ｋ，Ｃａ等を挙げることが出来る。この中では、ＬｉおよびＮａが特に好ましい。 Moreover, the thing which made the functional group into the salt especially from a viewpoint of pH is preferable. For example, it is an alkali metal salt, and examples of counter ions include Li, Na, K, and Ca. Of these, Li and Na are particularly preferred.
また、炭素表面を被覆する無機物としては、たとえばＣａＯ，Ｓｃ2Ｏ3，ＳｒＯ2，ＳｎＯ2，ＢａＯ，Ｌａ2Ｏ3，Ｎｄ2Ｏ3，ＷＯ3，Ａｌ2Ｏ3，ＳｉＯ2等の酸化物、またはＡｌＮ，ＧａＮ，ＳｉＮ等の窒化物、またはこれらの混合物を用いることができる。また、炭素表面を被覆する方法としてはたとえば溶液からの塗布法，蒸着法，ラングミュアブロジェット（ＬＢ）法，電解重合法，プラズマ重合法，ＣＶＤ（ｃｈｅｍｉｃａｌ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ）法，スパッタリング法などを用いることができる。Examples of the inorganic material covering the carbon surface include oxidation of CaO, Sc 2 O 3 , SrO 2 , SnO 2 , BaO, La 2 O 3 , Nd 2 O 3 , WO 3 , Al 2 O 3 , and SiO 2. Or a nitride such as AlN, GaN, SiN, or a mixture thereof. Further, as a method for coating the carbon surface, for example, a coating method from a solution, a vapor deposition method, a Langmuir Blodget (LB) method, an electrolytic polymerization method, a plasma polymerization method, a CVD (chemical vapor deposition) method, a sputtering method, or the like is used. Can do.
本発明の一実施形態における負極１２は、上記の負極活物質、バインダ及び集電体を含む。高レート充放電が必要な場合には、導電剤を添加することもある。
The
本発明の一実施形態で使用可能なポリマーが吸着した負極活物質（核材）としては、黒鉛を選択することができる。黒鉛は、黒鉛層間距離（ｄ002）が０．３３４ｎｍ以上０．３３８ｎｍ以下であることが好ましい。０．３３８ｎｍを超えると活物質の容量が小さく、電池の容量が小さくなってしまうため好ましくない。Graphite can be selected as the negative electrode active material (core material) on which the polymer usable in one embodiment of the present invention is adsorbed. The graphite preferably has a graphite interlayer distance (d 002 ) of 0.334 nm or more and 0.338 nm or less. If it exceeds 0.338 nm, the capacity of the active material is small, and the capacity of the battery becomes small.
負極活物質としての黒鉛は、リチウムイオンを化学的に吸蔵・放出可能な天然黒鉛、人造黒鉛、メソフェ−ズ炭素、膨張黒鉛、炭素繊維、気相成長法炭素繊維、ピッチ系炭素質材料、ニードルコークス、石油コークス、及びポリアクリロニトリル系炭素繊維等を原料として製造される。なお、上記の黒鉛層間距離（ｄ002）は、ＸＲＤ（Ｘ線粉末回折法）（Ｘ−Ｒａｙ Ｄｉｆｆｒａｃｔｉｏｎ Ｍｅｔｈｏｄ）等を用いて測定することができる。Graphite as the negative electrode active material is natural graphite, artificial graphite, mesophase carbon, expanded graphite, carbon fiber, vapor grown carbon fiber, pitch-based carbonaceous material, needle capable of chemically occluding and releasing lithium ions. Manufactured from coke, petroleum coke, polyacrylonitrile-based carbon fiber and the like. Note that the graphite interlayer distance (d 002) can be measured using the XRD (X-ray powder diffractometry) (X-Ray Diffraction Method) or the like.
負極活物質へのポリマーを吸着させる方法は以下の方法を用いることが出来る。但し、上記特徴を満たしているのであれば、その限りではない。 The following method can be used as a method of adsorbing the polymer to the negative electrode active material. However, this does not apply as long as the above characteristics are satisfied.
負極活物質の粒径は、負極活物質及びバインダから形成される負極合剤層の厚さ以下にすることが望ましい。負極活物質の粉末中に負極合剤層厚さ以上のサイズを有する粗粒がある場合、予めふるい分級や風流分級等により粗粒を除去し、負極合剤層の厚さ以下の粒子を使用することが好ましい。 The particle size of the negative electrode active material is desirably set to be equal to or less than the thickness of the negative electrode mixture layer formed from the negative electrode active material and the binder. If the negative electrode active material powder has coarse particles with a size greater than or equal to the thickness of the negative electrode mixture layer, remove the coarse particles in advance by sieving, airflow classification, etc., and use particles smaller than the thickness of the negative electrode mixture layer It is preferable to do.
具体的な粒径としては、レーザ回折／散乱式粒度分布測定装置により求めた平均粒径が、３μｍ以上３０μｍ以下であることが好ましく、さらに３μｍ以上２５μｍ以下、特に５μｍ以上２０μｍ以下であることが好ましい平均粒径が３０μｍを超える場合、電極に凹凸ができやすくなるため、電池特性が低下する場合がある。また、３μｍ未満である場合、黒鉛がつぶれ難くなるため、密度を上げにくくなる傾向がある。なお、粒度分布は界面活性剤を含んだ精製水に試料を分散させ、レーザ回折／散乱式粒度分布測定装置で測定することができ、平均粒径は累積５０％粒径（５０％Ｄ）として算出される。 The specific particle size is preferably 3 μm or more and 30 μm or less, more preferably 3 μm or more and 25 μm or less, and particularly preferably 5 μm or more and 20 μm or less. When the preferable average particle diameter exceeds 30 μm, the electrode characteristics are likely to be uneven, and thus the battery characteristics may be deteriorated. On the other hand, when the thickness is less than 3 μm, graphite is not easily crushed, so that the density tends to be difficult to increase. The particle size distribution can be measured by dispersing a sample in purified water containing a surfactant and measuring with a laser diffraction / scattering type particle size distribution measuring device, and the average particle size is 50% cumulative (50% D). Calculated.
０．１ｍ2／ｇ未満の場合は、負極活物質とリチウムイオンとの反応面積が減少するため、充放電特性が悪化する場合がある。また、１０ｍ2／ｇを超える場合は、電解質との反応が起こりやすくなるため、不可逆容量が増大してしまい、寿命特性が悪化する恐れがある。If it is less than 0.1 m 2 / g, the reaction area between the negative electrode active material and lithium ions decreases, and the charge / discharge characteristics may deteriorate. On the other hand, if it exceeds 10 m 2 / g, the reaction with the electrolyte tends to occur, so that the irreversible capacity increases and the life characteristics may be deteriorated.
吸着させるポリマーは、吸着均一性を高める観点から予め純水に溶かして水溶液にしておくのが好ましい。ポリマー水溶液の作製方法は、特に限定されないが、溶け残りは不均一化の原因となるため、溶け残りが無いように注意する必要がある。例えば、プロペラやウエーブロータで撹拌しながら少量ずつ添加する事で溶解することが出来る。この際、必要に応じて熱をかけても構わない。また、溶解後の水溶液の濾過を実施しても構わない。ポリマー水溶液の濃度は特に限定されないが、溶け残りの観点を考えると、０．５〜２．０質量％前後である事が好ましい。濃度が薄すぎる、もしくは濃すぎる場合、均一吸着性が低下する。 The polymer to be adsorbed is preferably dissolved in pure water in advance from the viewpoint of improving adsorption uniformity. The method for preparing the polymer aqueous solution is not particularly limited, but since the undissolved residue causes non-uniformity, care must be taken so that there is no undissolved residue. For example, it can be dissolved by adding little by little while stirring with a propeller or a wave rotor. At this time, heat may be applied as necessary. Moreover, you may implement filtration of the aqueous solution after melt | dissolution. Although the density | concentration of polymer aqueous solution is not specifically limited, Considering the viewpoint of undissolved, it is preferable that it is about 0.5-2.0 mass%. If the concentration is too light or too dark, the uniform adsorptivity is reduced.
負極活物質である炭素材料に、作製したポリマー水溶液を添加し、ディスパー等を用いて撹拌する事で、ポリマーを吸着させる。この際、適宜純水を加えて、流動性を持たせる事が好ましい。十分に撹拌、分散させた後、炭素材料含有水溶液を恒温槽内に保持することで、乾燥させる。この際、温度は８０℃以下で行うことが好ましい。１００℃前後のような、水が沸騰する高温で処理すると吸着したポリマーの均一性が低下する恐れがあるため、好ましくない。 The prepared polymer aqueous solution is added to the carbon material which is the negative electrode active material, and the polymer is adsorbed by stirring with a disper or the like. At this time, it is preferable that pure water is appropriately added to provide fluidity. After sufficiently stirring and dispersing, the carbon material-containing aqueous solution is dried by holding it in a thermostatic bath. At this time, the temperature is preferably 80 ° C. or lower. Treatment at a high temperature such as around 100 ° C. where water is boiling is not preferred because the uniformity of the adsorbed polymer may be reduced.
水分がある程度気化した段階で、高温や、真空下に保持する事で更に水分を飛ばす工程を加えても構わない。但し、ポリマーが分解するような高温は好ましくない。 At the stage when the moisture is vaporized to some extent, a step of further removing moisture by holding it under high temperature or under vacuum may be added. However, a high temperature at which the polymer decomposes is not preferable.
得られた負極材は、解砕することが好ましい。解砕は、一般的なリチウムイオン二次電池用黒鉛材料の方法であれば特に限定されない。別の手法として、負極合剤スラリーの調整時に、ポリマーを添加する方法を用いても構わない。事後吸着は製造プロセスとの整合性を確保する必要があるが、事前吸着の場合に比べて製造コストを小さくする事が出来るメリットがある。 The obtained negative electrode material is preferably crushed. Crushing is not particularly limited as long as it is a general method for a graphite material for a lithium ion secondary battery. As another method, a method of adding a polymer at the time of preparing the negative electrode mixture slurry may be used. Although post-adsorption needs to ensure consistency with the manufacturing process, there is an advantage that the manufacturing cost can be reduced as compared with the case of pre-adsorption.
負極１２の作製方法は、特に限定されるものではないが、例えば、負極活物質、増粘剤、水溶性バインダ、及び事後吸着の場合、ポリマーを、溶媒中にいれ、ボールミル、プラネタリーミキサー等の一般的な混錬分散方法を用いてよく混練分散して、負極合剤スラリーを作製する。続いて、この負極合剤スラリーを、塗布機を用いて銅等の金属箔からなる集電体上に塗布し、例えば１００℃前後の適当な温度にて真空乾燥し、プレス機を用いて圧縮成形した後に所望の大きさに切断又は打ち抜いて、目的の負極１２を作製することができる。
The production method of the
負極合剤スラリーを調製する際の溶媒としては、特に限定されないが、例えば、純水、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、エチレングリコール、トルエン、キシレン等が挙げられる。 Although it does not specifically limit as a solvent at the time of preparing a negative mix slurry, For example, a pure water, N-methyl-2-pyrrolidone (NMP), ethylene glycol, toluene, xylene etc. are mentioned.
水溶性バインダとしては、アクリロニトリル−ブタジエンゴム（ＮＢＲ）やスチレン−ブタジエンゴム（ＳＢＲ）等の非フッ素系有機重合体を負極合剤に添加してもよい。更に増粘剤として、水溶性多糖類を併用する事が好ましい。水溶性多糖類としては、メチルセルロース、エチルセルロース、アセチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、でんぷん、カラギナン、プルラン、グアーガム、ザンサンガム（キサンタンガム）、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース等が挙げられる。これらのうち、一部を塩にしてもよい。この中では、特にカルボキシメチルセルロースのナトリウム塩が好ましい。これらの化合物は単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 As the water-soluble binder, a non-fluorine organic polymer such as acrylonitrile-butadiene rubber (NBR) or styrene-butadiene rubber (SBR) may be added to the negative electrode mixture. Further, it is preferable to use a water-soluble polysaccharide in combination as a thickener. Examples of the water-soluble polysaccharide include methylcellulose, ethylcellulose, acetylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch, carrageenan, pullulan, guar gum, xanthan gum (xanthan gum), hydroxypropylcellulose, hydroxypropylmethylcellulose and the like. Some of these may be salted. Among these, a sodium salt of carboxymethyl cellulose is particularly preferable. These compounds may be used alone or in combination of two or more.
負極１２の集電体には、厚さが１０〜１００μｍの銅箔、厚さが１０〜１００μｍで孔径０．１〜１０ｍｍの銅製穿孔箔、エキスパンドメタル、又は発泡金属板等が用いられる。銅の他に、ステンレス、チタン、又はニッケル等の材質も適用可能である。本発明では、材質、形状、製造方法等に制限されることなく、任意の集電体を使用することができる。
For the current collector of the
負極活物質、バインダ、及び有機溶媒を混合した負極スラリーを、ドクターブレード法、ディッピング法、又はスプレー法等によって集電体へ付着させた後、有機溶媒を乾燥させ、ロールプレスによって加圧成形することにより、負極を作製することができる。また、塗布から乾燥までを複数回行うことにより、多層合剤層を集電体に形成させることも可能である。 A negative electrode slurry in which a negative electrode active material, a binder, and an organic solvent are mixed is attached to a current collector by a doctor blade method, a dipping method, a spray method, or the like, and then the organic solvent is dried and pressure-molded by a roll press. Thereby, a negative electrode can be produced. Moreover, it is also possible to form a multilayer mixture layer on a current collector by carrying out a plurality of times from application to drying.
負極には、上記の黒鉛、非黒鉛炭素等とは別の活物質として、リチウムと合金を形成する材料又は金属間化合物を形成する材料が混合されていても良い。例えば、アルミニウム、シリコン、スズ等の金属及びこれらの合金、リチウム含有の遷移金属窒化物Ｌｉ(3-x)ＭxＮ、ケイ素の低級酸化物ＬｉxＳｉＯy（０≦ｘ、０＜ｙ＜２）、及びスズの低級酸化物ＬｉxＳｎＯy（０≦ｘ、０＜ｙ＜２）が挙げられる。上記の材料以外の材料が混合する材料として、選択しても構わない。The negative electrode may be mixed with a material that forms an alloy with lithium or a material that forms an intermetallic compound as an active material different from the above-described graphite, non-graphitic carbon, and the like. For example, metals such as aluminum, silicon and tin and alloys thereof, lithium-containing transition metal nitrides Li (3-x) M x N, lower oxides of silicon Li x SiO y (0 ≦ x, 0 <y < 2), and a lower oxide of tin, Li x SnO y (0 ≦ x, 0 <y <2). You may select as a material which materials other than said material mix.
＜正極＞
正極１０は、正極活物質、導電剤、バインダ、及び集電体から構成される。正極活物質を例示すると、ＬｉＣｏＯ2、ＬｉＮｉＯ2、及びＬｉＭｎ2Ｏ4が代表例である。他に、ＬｉＭｎＯ3、ＬｉＭｎ2Ｏ3、ＬｉＭｎＯ2、Ｌｉ4Ｍｎ5Ｏ12、ＬｉＭｎ2-xＭｘＯ2（ただし、Ｍ＝Ｃｏ、Ｎｉ、Ｆｅ、Ｃｒ、Ｚｎ、Ｔｉからなる群から選ばれる少なくとも１種、ｘ＝０．０１〜０．２）、Ｌｉ2Ｍｎ3ＭＯ8（ただし、Ｍ＝Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎからなる群から選ばれる少なくとも１種）、Ｌｉ1-xＡxＭｎ2Ｏ4（ただし、Ａ＝Ｍｇ、Ｂ、Ａｌ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｒ、Ｚｎ、Ｃａからなる群から選ばれる少なくとも１種、ｘ＝０．０１〜０．１）、ＬｉＮｉ1-xＭxＯ2（ただし、Ｍ＝Ｃｏ、Ｆｅ、Ｇａからなる群から選ばれる少なくとも１種、ｘ＝０．０１〜０．２）、ＬｉＦｅＯ2、Ｆｅ2（ＳＯ4）3、ＬｉＣｏ1-xＭxＯ2（ただし、Ｍ＝Ｎｉ、Ｆｅ、Ｍｎからなる群から選ばれる少なくとも１種、ｘ＝０．０１〜０．２）、ＬｉＮｉ1-xＭxＯ2（ただし、Ｍ＝Ｍｎ、Ｆｅ、Ｃｏ、Ａｌ、Ｇａ、Ｃａ、Ｍｇからなる群から選ばれる少なくとも１種、ｘ＝０．０１〜０．２）、Ｆｅ（ＭｏＯ4）3、ＦｅＦ3、ＬｉＦｅＰＯ4、及びＬｉＭｎＰＯ4等を列挙することができる。<Positive electrode>
The
正極活物質の粒径は、正極活物質、導電剤、及びバインダから形成される合剤層の厚さ以下になるように通常は規定される。正極活物質の粉末中に合剤層厚さ以上のサイズを有する粗粒がある場合、予めふるい分級や風流分級等により粗粒を除去し、合剤層厚さ以下の粒子を作製することが好ましい。 The particle size of the positive electrode active material is usually defined so as to be equal to or less than the thickness of the mixture layer formed from the positive electrode active material, the conductive agent, and the binder. When there are coarse particles having a size equal to or greater than the thickness of the mixture layer in the positive electrode active material powder, the coarse particles can be removed in advance by sieving classification or wind classification to produce particles having a thickness of the mixture layer thickness or less. preferable.
また、正極活物質は、一般に酸化物系であるために電気抵抗が高いので、電気伝導性を補うための炭素粉末からなる導電剤を利用する。正極活物質及び導電剤はともに通常は粉末であるので、粉末にバインダを混合して、粉末同士を結合させると同時に集電体へ接着させることができる。 In addition, since the positive electrode active material is generally oxide-based and has high electrical resistance, a conductive agent made of carbon powder for supplementing electrical conductivity is used. Since both the positive electrode active material and the conductive agent are usually powders, a binder can be mixed with the powders, and the powders can be bonded together and simultaneously bonded to the current collector.
正極１０の集電体には、厚さが１０〜１００μｍのアルミニウム箔、厚さが１０〜１００μｍで孔径が０．１〜１０ｍｍのアルミニウム製穿孔箔、エキスパンドメタル、又は発泡金属板等が用いられる。アルミニウムの他に、ステンレスやチタン等の材質も適用可能である。本発明では、材質、形状、製造方法等に制限されることなく、任意の集電体を使用することができる。
For the current collector of the
正極活物質、導電剤、バインダ、及び有機溶媒を混合した正極スラリーを、ドクターブレード法、ディッピング法、又はスプレー法等によって集電体へ付着させた後、有機溶媒を乾燥させ、ロールプレスによって加圧成形することにより、正極１０を作製することができる。また、塗布から乾燥までを複数回行うことにより、複数の合剤層を集電体に積層化させることも可能である。
A positive electrode slurry in which a positive electrode active material, a conductive agent, a binder, and an organic solvent are mixed is attached to a current collector by a doctor blade method, a dipping method, or a spray method, and then the organic solvent is dried and applied by a roll press. The
＜セパレータ＞
以上の方法で作製した正極１０及び負極１２の間にセパレータ１１を挿入し、正極１０及び負極１２の短絡を防止する。セパレータ１１には、ポリエチレン、ポリプロピレン等からなるポリオレフィン系高分子シート、又はポリオレフィン系高分子と４フッ化ポリエチレンを代表とするフッ素系高分子シートを溶着させた２層構造等を使用することが可能である。電池温度が高くなったときにセパレータ１１が収縮しないように、セパレータ１１の表面にセラミックス及びバインダの混合物を薄層状に形成してもよい。これらのセパレータ１１は、電池の充放電時にリチウムイオンを透過させる必要があるため、一般に細孔径が０．０１〜１０μｍ、気孔率が２０〜９０％であれば、リチウムイオン二次電池に使用可能である<Separator>
The
＜電解質＞
本発明の一実施形態で使用可能な電解液の代表例として、エチレンカーボネートにジメチルカーボネート、ジエチルカーボネート、又はエチルメチルカーボネート等を混合した溶媒に、電解質として六フッ化リン酸リチウム（ＬｉＰＦ6）、又はホウフッ化リチウム（ＬｉＢＦ4）を溶解させた溶液がある。本発明は、溶媒や電解質の種類、溶媒の混合比に制限されることなく、他の電解液も利用可能である。<Electrolyte>
As a representative example of an electrolyte solution that can be used in an embodiment of the present invention, a solvent obtained by mixing ethylene carbonate with dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate, lithium hexafluorophosphate (LiPF 6 ) as an electrolyte, Alternatively, there is a solution in which lithium borofluoride (LiBF 4 ) is dissolved. The present invention is not limited to the type of solvent and electrolyte, and the mixing ratio of solvents, and other electrolytes can be used.
なお、電解液に使用可能な非水溶媒の例としては、プロピレンカーボネート、エチレンカーボネート（ＥＣ）、ブチレンカーボネート、ビニレンカーボネート、γ−ブチロラクトン、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、メチルエチルカーボネート、１、２−ジメトキシエタン、２−メチルテトラヒドロフラン、ジメチルスルフォキシド、１、３−ジオキソラン、ホルムアミド、ジメチルホルムアミド、プロピオン酸メチル、プロピオン酸エチル、リン酸トリエステル、トリメトキシメタン、ジオキソラン、ジエチルエーテル、スルホラン、３−メチル−２−オキサゾリジノン、テトラヒドロフラン、１、２−ジエトキシエタン、クロルエチレンカーボネート、又はクロルプロピレンカーボネート等の非水溶媒がある。本発明の電池に内蔵される正極１０又は負極１２上で分解しなければ、これ以外の溶媒を用いてもよい。
Examples of non-aqueous solvents that can be used in the electrolyte include propylene carbonate, ethylene carbonate (EC), butylene carbonate, vinylene carbonate, γ-butyrolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate. 1,2-dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphoric acid triester, trimethoxymethane, dioxolane, diethyl ether , Sulfolane, 3-methyl-2-oxazolidinone, tetrahydrofuran, 1,2-diethoxyethane, chloroethylene carbonate, or chloropropylene carbonate There is. Other solvents may be used as long as they do not decompose on the
また、電解質の例としては、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＣＦ3ＣＯ2、ＬｉＡｓＦ6、ＬｉＳｂＦ6、又はリチウムトリフルオロメタンスルホンイミドで代表されるリチウムのイミド塩等、多種類のリチウム塩がある。これらの塩を、上記の溶媒に溶解してできた非水電解液を電池用電解液として使用することができる。本実施形態に係る電池が有する正極１０及び負極１２上で分解しなければ、これ以外の電解質を用いてもよい。In addition, examples of the electrolyte, LiPF 6, LiBF 4, LiClO 4, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, or imide salts such as lithium represented by lithium trifluoromethane sulfonimide, multi There are different types of lithium salts. A nonaqueous electrolytic solution obtained by dissolving these salts in the above-mentioned solvent can be used as a battery electrolytic solution. An electrolyte other than this may be used as long as it does not decompose on the
固体高分子電解質（ポリマー電解質）を用いる場合には、ポリエチレンオキシド、ポリアクリロニトリル、ポリフッ化ビニリデン、ポリメタクリル酸メチル、ポリヘキサフルオロプロピレン、ポリエチレンオキサイド等のイオン伝導性ポリマーを電解質に用いることができる。これらの固体高分子電解質を用いた場合、セパレータ１１を省略することができる利点がある。
When a solid polymer electrolyte (polymer electrolyte) is used, an ion conductive polymer such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polyhexafluoropropylene, and polyethylene oxide can be used for the electrolyte. When these solid polymer electrolytes are used, there is an advantage that the
さらに、イオン性液体を用いることができる。例えば、１−ｅｔｈｙｌ−３−ｍｅｔｈｙｌｉｍｉｄａｚｏｌｉｕｍ ｔｅｔｒａｆｌｕｏｒｏｂｏｒａｔｅ（ＥＭＩ−ＢＦ４）、リチウム塩ＬｉＮ（ＳＯ2ＣＦ3）2（ＬｉＴＦＳＩ）とトリグライムとテトラグライムとの混合錯体、環状四級アンモニウム系陽イオン（Ｎ−ｍｅｔｈｙｌ−Ｎ−ｐｒｏｐｙｌｐｙｒｒｏｌｉｄｉｎｉｕｍが例示される。）、及びイミド系陰イオン（ｂｉｓ（ｆｌｕｏｒｏｓｕｌｆｏｎｙｌ）ｉｍｉｄｅが例示される。）より、正極１０及び負極１２にて分解しない組み合わせを選択して、本実施形態に係る電池に用いることができる。Furthermore, an ionic liquid can be used. For example, 1-ethyl-3-methylimidazole tetrafluoroborate (EMI-BF4), a mixed salt of a lithium salt LiN (SO 2 CF 3 ) 2 (LiTFSI), triglyme and tetraglyme, a cyclic quaternary ammonium cation (N-methyl) -N-propylpyrrolidinium is exemplified) and an imide-based anion (example is bis (fluorosulfonyl) imide), a combination that does not decompose at the
本発明の一実施形態に係るリチウムイオン二次電池は、例えば、上述のような負極と正極とをセパレータを介して対向して配置し、電解質を注入することによって製造することができる。本発明の一実施形態に係るリチウムイオン二次電池の構造は特に限定されないが、通常、正極及び負極とそれらを隔てるセパレータとを捲回して捲回式電極群にするか、又は正極、負極及びセパレータを積層させて積層型の電極群とすることができる。 The lithium ion secondary battery according to an embodiment of the present invention can be manufactured by, for example, disposing the above-described negative electrode and positive electrode facing each other via a separator and injecting an electrolyte. The structure of the lithium ion secondary battery according to one embodiment of the present invention is not particularly limited. Usually, the positive electrode and the negative electrode and the separator separating them are wound into a wound electrode group, or the positive electrode, the negative electrode, and the negative electrode A separator can be laminated to form a laminated electrode group.
以下、実施例及び比較例を示して本発明をさらに詳細に説明する。なお、以下の実施例は一例であり、これらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following Examples are examples and are not limited to these.
負極活物質の合成手順を示す。まずオートクレーブを用いて，石炭系コールタールを４００℃で熱処理し生コークスを得た。この生コークスを粉砕した後，２８００℃にて不活性雰囲気中でカ焼を行い，炭素層間距離（ｄ002）が０.３３５ｎｍの炭素材料を得た。この炭素材料を分級機付きの衝撃破砕機を用いて粉砕し，３００メッシュの篩にて粗粉を除去して炭素粒子とした。その際の平均粒径は１６．６μｍで比表面積は５．８ｍ2／ｇであった。The synthesis procedure of the negative electrode active material is shown. First, using an autoclave, coal-based coal tar was heat-treated at 400 ° C. to obtain raw coke. The raw coke was pulverized and calcined at 2800 ° C. in an inert atmosphere to obtain a carbon material having a carbon interlayer distance (d 002 ) of 0.335 nm. The carbon material was pulverized using an impact crusher equipped with a classifier, and coarse particles were removed with a 300 mesh sieve to obtain carbon particles. At that time, the average particle diameter was 16.6 μm and the specific surface area was 5.8 m 2 / g.
この黒鉛にポリマーを吸着させた。吸着させる高分子には、ポリビニルスルホン酸Ｎａを用いた。水溶液濃度１．０質量％になるように純水にポリビニルスルホン酸Ｎａを添加し、ウエーブロータで８ｈ撹拌し溶液とした。 A polymer was adsorbed on the graphite. Polyvinylsulfonic acid Na was used as the polymer to be adsorbed. Polyvinylsulfonic acid Na was added to pure water so that the aqueous solution concentration was 1.0% by mass, and the solution was stirred with a wave rotor for 8 hours.
前述した黒鉛粒子１００ｇに対し、ポリマーの固形分比が１質量％になるように、ポリビニルスルホン酸Ｎａ水溶液１００ｇを撹拌しながら添加した。装置は、プラネタリーミキサーを用い、回転速度２０ｒｐｍで混練分散した後、ディスパーを用い、５０００ｒｐｍで３ｈ撹拌し、スラリー化した。 100 g of polyvinyl sulfonate aqueous solution was added with stirring so that the solid content ratio of the polymer was 1% by mass with respect to 100 g of the graphite particles described above. The apparatus was kneaded and dispersed at a rotational speed of 20 rpm using a planetary mixer, and then stirred at 5000 rpm for 3 hours using a disper to make a slurry.
得られたスラリーを８０℃で３ｈ保持して乾燥後、１００℃真空乾燥を４ｈ実施した。 The obtained slurry was held at 80 ° C. for 3 hours and dried, followed by vacuum drying at 100 ° C. for 4 hours.
得られた塊状黒鉛をミキサーで解砕し、目開き５０μｍの篩を用いて分級し、これをリチウムイオン二次電池用負極活物質とした。その際の平均粒径は１７．８μｍであり、比表面積は３．２ｍ2／ｇであった。The obtained massive graphite was crushed with a mixer and classified using a sieve having an opening of 50 μm, and this was used as a negative electrode active material for a lithium ion secondary battery. At that time, the average particle size was 17.8 μm, and the specific surface area was 3.2 m 2 / g.
正極活物質の合成手順を示す。原料として酸化ニッケル，酸化マンガン，酸化コバルトを使用し，原子比でＮｉ：Ｍｎ：Ｃｏ比が１：１：１となるように秤量し，湿式粉砕機で粉砕混合した。次に，バインダとしてポリビニルアルコール（ＰＶＡ）を加えた粉砕混合粉を噴霧乾燥機で造粒した。得られた造粒粉末を高純度アルミナ容器に入れ，ＰＶＡを蒸発させるため６００℃で１２時間の仮焼成を行い，空冷後解砕した。さらに，解砕粉にＬｉ：遷移金属（Ｎｉ，Ｍｎ，Ｃｏ）の原子比が１：１：１ となるよう水酸化リチウム一水和物を添加し，充分混合した。この混合粉末を高純度アルミナ容器に入れて９００℃で６時間の本焼成を行った。得られた正極活物質をボールミルで解砕分級した。この正極活物質の平均粒径は６μｍであった。 The synthesis procedure of the positive electrode active material is shown. Nickel oxide, manganese oxide, and cobalt oxide were used as raw materials, weighed so that the atomic ratio of Ni: Mn: Co was 1: 1: 1, and pulverized and mixed with a wet pulverizer. Next, the pulverized mixed powder to which polyvinyl alcohol (PVA) was added as a binder was granulated with a spray dryer. The obtained granulated powder was put into a high-purity alumina container, calcined at 600 ° C. for 12 hours to evaporate PVA, air-cooled and crushed. Further, lithium hydroxide monohydrate was added to the pulverized powder so that the atomic ratio of Li: transition metal (Ni, Mn, Co) was 1: 1: 1 and mixed well. This mixed powder was put into a high-purity alumina container and subjected to main firing at 900 ° C. for 6 hours. The obtained positive electrode active material was pulverized and classified with a ball mill. The average particle diameter of this positive electrode active material was 6 μm.
本実施例の炭素材料における炭素００２面の面間隔ｄ002はリガク製Ｘ線回折装置ＲＵ２００Ｂを用いて測定した。Ｘ線源には、Ｃｕを用い回折確度はＳｉを用いて補正を行った。測定により得たピークをプロファイルフィッティングすることにより、ブラッグの式を用いて算出することが出来る。Plane spacing d 002 of the carbon 002 plane of the carbon material of this example was measured using a Rigaku X-ray diffractometer RU200B. As the X-ray source, Cu was used and diffraction accuracy was corrected using Si. It is possible to calculate using the Bragg equation by profile fitting the peak obtained by the measurement.
実施例における材料の粒径（５０％Ｄ）は（株）堀場製作所製レーザ回折／散乱式粒度分布測定装置ＬＡ−９２０を用いて調べた。光源としては，Ｈｅ−Ｎｅレーザ１ｍＷを用い，炭素粒子の分散媒はイオン交換水に界面活性剤を２滴いれた物とした。予め５分以上超音波処理を行い，更に測定中も超音波処理を行って，凝集を防ぎつつ測定を行った。測定結果の累積５０％粒径（５０％Ｄ）を平均粒径とした。
The particle size (50% D) of the material in the examples was examined using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd. A He—
実施例におけるリチウムイオン二次電池の負極活物質である炭素材料の比表面積は，炭素材料を１２０℃で３時間真空乾燥した後，日本ベル株式会社製ＢＥＬＳＯＲＰ−ｍｉｎｉを用い，７７Ｋでの窒素吸着を用いて平衡時間３００秒で測定した吸着等温線をＢＥＴ法で解析し求めた。 The specific surface area of the carbon material, which is the negative electrode active material of the lithium ion secondary battery in the example, was obtained by vacuum-drying the carbon material at 120 ° C. for 3 hours, and then using a BELSORP-mini made by Nippon Bell Co., Ltd. for nitrogen adsorption at 77K. The adsorption isotherm measured with an equilibration time of 300 seconds was analyzed by the BET method.
本実施例における体積抵抗率は三菱化学製ロレスターＧＰ、ＭＣＰ-T６１０を用いて測定した。粉体抵抗は、圧力を１ｋＮごとに２０ｋＮまで測定した。 The volume resistivity in the present Example was measured using Mitsubishi Chemical Lorester GP, MCP-T610. The powder resistance was measured up to a pressure of 20 kN per 1 kN.
次に，リチウムイオン二次電池を作成した。まず，正極を作製した。正極活物質８５．０重量部に導電材として粉末状炭素とアセチレンブラックをそれぞれ７．０重量部と２．０重量部加え，あらかじめバインダとして６．０重量部のＰＶＤＦをＮＭＰに溶解した溶液を加えて，さらにプラネタリ−ミキサーで混合し正極合剤スラリーとした。このスラリーを塗布機で厚さ２０μｍのアルミニウム箔の両面に均一かつ均等に塗布した塗布後ロールプレス機により電極密度が２．５５ｇ／ccになるように圧縮成形し，正極とした。 Next, a lithium ion secondary battery was created. First, a positive electrode was produced. 7.0 parts by weight and 2.0 parts by weight of powdered carbon and acetylene black as conductive materials were added to 85.0 parts by weight of the positive electrode active material, respectively, and a solution in which 6.0 parts by weight of PVDF was previously dissolved in NMP as a binder was added. In addition, the mixture was further mixed with a planetary mixer to obtain a positive electrode mixture slurry. This slurry was applied uniformly and evenly on both sides of an aluminum foil having a thickness of 20 μm with a coating machine, and then compression-molded with a roll press machine so that the electrode density was 2.55 g / cc to obtain a positive electrode.
次に，負極を作製した。負極活物質としての前記黒鉛９７．０重量部に、ＣＭＣ（カルボメチルセルロース）の１％水溶液の固形分１．５重量部相当量と、ＳＢＲの４０％水溶液の固形分１．５重量部相当量を加え、さらにプラネタリ−ミキサーで混合し負極合剤スラリーを調製した。このスラリーを、厚さ１０μｍの圧延銅箔からなる集電体の両面に塗布機で均一かつ均等に塗布した塗布後、ロールプレス機で圧縮成形し、負極とした。 Next, a negative electrode was produced. 97.0 parts by weight of the graphite as the negative electrode active material is equivalent to 1.5 parts by weight of a solid content of a 1% aqueous solution of CMC (carbomethylcellulose) and 1.5 parts by weight of a solid content of a 40% aqueous solution of SBR. Was further mixed with a planetary mixer to prepare a negative electrode mixture slurry. The slurry was applied uniformly and evenly on both sides of a current collector made of rolled copper foil having a thickness of 10 μm with a coating machine, and then compression-molded with a roll press to obtain a negative electrode.
まず，正極と負極を所望の大きさに裁断し，未塗布部にそれぞれ集電タブを超音波溶接した。集電タブはそれぞれ正極にはアルミニウムのリード片，負極にはニッケルのリード片を用いた。その後，厚み３０μｍのセパレータを多孔性のポリエチレンフィルムで正極と負極に挟みながら捲回したこの捲回体を電池缶に挿入し，負極タブを電池缶の缶底に抵抗溶接により接続し，正極タブには正極蓋を超音波溶接により接続した。体積比がＥＣ，ＤＭＣ，ＤＥＣの体積比１：１：１の混合溶媒に１モル／リットルのＬｉＰＦ6を溶解させた電解液を注液し，その後，正極蓋を電池缶にかしめて密封し，リチウムイオン二次電池を得た。First, the positive electrode and the negative electrode were cut into desired sizes, and current collecting tabs were ultrasonically welded to the uncoated portions. Each of the current collecting tabs used an aluminum lead piece for the positive electrode and a nickel lead piece for the negative electrode. After that, the rolled body obtained by winding a separator having a thickness of 30 μm between a positive electrode and a negative electrode with a porous polyethylene film is inserted into the battery can, and the negative electrode tab is connected to the bottom of the battery can by resistance welding. The positive electrode lid was connected to by ultrasonic welding. An electrolyte solution in which 1 mol / liter of LiPF 6 is dissolved in a mixed solvent having a volume ratio of 1: 1, 1: 1 by volume ratio of EC, DMC, and DEC is injected, and then the positive electrode lid is caulked and sealed in a battery can. A lithium ion secondary battery was obtained.
まず，電池の直流抵抗（ＤＣＲ）を測定し、電池の出力密度を求めた。作製した電池を常温（２５℃）前後で０.３Ｃ相当の電流で４．１Ｖまで充電し，その後４．１Ｖで電流が０.０３Ｃになるまで定電圧充電を行った。３０分休止後に０.３Ｃ相当の定電流で２．７Ｖまで定電流放電を行った。これを４サイクル行い初期化し、４サイクル目の放電容量より電池重量辺りの容量密度ｍＡｈ／ｇを求めたさらに０．３Ｃで３．６Ｖまで定電流充電行った後，電流４ＣＡ，８ＣＡ，１２ＣＡ，１６ＣＡの電流値で１０秒間放電した。この時の電圧値を求めて，これを２.５Ｖまで外挿したときの限界電流から出力密度を求めた。結果を表１に示す。 First, the direct current resistance (DCR) of the battery was measured to determine the output density of the battery. The manufactured battery was charged to 4.1 V at a current equivalent to 0.3 C around room temperature (25 ° C.), and then constant voltage charging was performed until the current became 0.03 C at 4.1 V. After a 30-minute pause, constant current discharge was performed up to 2.7 V with a constant current corresponding to 0.3 C. This was repeated for 4 cycles, the capacity density mAh / g around the weight of the battery was determined from the discharge capacity at the 4th cycle, and further charged at a constant current to 3.6 V at 0.3 C, and then currents 4CA, 8CA, 12CA, The battery was discharged for 10 seconds at a current value of 16 CA. The voltage value at this time was obtained, and the output density was obtained from the limit current when this was extrapolated to 2.5V. The results are shown in Table 1.
次に、２５℃で、５００回の充放電サイクルを行った。各サイクルにおいては、１Ｃ相当の電流で４．１Ｖまで充電し、その後４．１Ｖで電流が０．０３Ｃになるまで定電圧充電を行った。放電は、１Ｃ相当の電流で２．７Ｖまで放電した。充放電の間には休止を３０分行った。 Next, 500 charge / discharge cycles were performed at 25 ° C. In each cycle, the battery was charged to 4.1 V with a current corresponding to 1 C, and then constant voltage charging was performed until the current became 0.03 C at 4.1 V. Discharge was discharged to 2.7 V with a current corresponding to 1 C. During charging and discharging, a pause was performed for 30 minutes.
次いで、サイクルさせた電池を信頼性試験として電池の圧潰試験を行った。充電電圧４．１Ｖ、充電時間２時間、制限電流８００ｍＡの定電圧・定電流充電を行い、電池の圧潰試験を行った。直径６ｍｍの円柱の丸棒を用いて、この丸棒が電池の外寸が最も長くなる方向に対して垂直になる方向から電池の中央部に押しつけて、電池の厚みが半分になるまで潰した。この際結果を変化無し，弁作動のみ，弁作動＋発煙，弁作動＋発煙＋発火に分類した。ここで弁作動のみとは安全弁が開いた状態，弁作動＋発煙は安全弁が開いて同時に気体が噴出した状態，弁作動＋発煙＋発火は気体が電池から噴出し，発火した状態である。また，各表では変化なしは「変化無し」，弁作動のみを「弁作動」，弁作動＋発煙を「発煙」，弁作動＋発煙＋発火を「発火」と記載した。結果を表１に示す。 Subsequently, the battery was subjected to a crush test using the cycled battery as a reliability test. A constant voltage / constant current charge with a charging voltage of 4.1 V, a charging time of 2 hours and a limiting current of 800 mA was performed, and a battery crushing test was performed. Using a cylindrical round bar with a diameter of 6 mm, this round bar was pressed against the center of the battery from the direction perpendicular to the direction in which the outer dimension of the battery was the longest, and crushed until the thickness of the battery was halved. . The results were classified as no change, valve operation only, valve operation + smoke, valve operation + smoke + ignition. Here, only the valve operation is a state in which the safety valve is open, valve operation + smoke is a state in which the safety valve is open and gas is simultaneously ejected, and valve operation + smoke + ignition is a state in which gas is ejected from the battery and ignited. In each table, “no change” indicates no change, “valve operation” indicates only valve operation, “smoke” indicates valve operation + smoke, and “ignition” indicates valve operation + smoke + ignition. The results are shown in Table 1.
また信頼性試験として過充電試験をしてから電池の圧潰試験を行った。充電電圧を４．３Ｖに変更した以外は上述の方法と同様の手順で行った。結果を表１に示す。 In addition, an overcharge test was performed as a reliability test, and then a battery crush test was performed. The procedure was the same as that described above except that the charging voltage was changed to 4.3V. The results are shown in Table 1.
ポリビニルスルホン酸Ｎａをポリビニルスルホン酸に変更したこと以外は、同様に行った。 It carried out similarly except having changed polyvinyl sulfonic acid Na into polyvinyl sulfonic acid.
ポリビニルスルホン酸Ｎａの水溶液濃度を０．５質量％にし、黒鉛と混合する際の添加量を２００ｇにしたこと以外は、実施例１と同様に行った。 The same procedure as in Example 1 was performed except that the concentration of the aqueous solution of sodium polyvinyl sulfonate was 0.5% by mass and the amount added when mixing with graphite was 200 g.
ポリビニルスルホン酸Ｎａの水溶液濃度を２．０質量％にし、黒鉛と混合する際の添加量を５０ｇにしたこと以外は、実施例１と同様に行った。 The same procedure as in Example 1 was performed except that the concentration of the aqueous solution of sodium polyvinyl sulfonate was 2.0% by mass and the addition amount when mixing with graphite was 50 g.
黒鉛に対するポリマーの添加量を、ポリマー固形分比を２質量％になるように、ポリビニルスルホン酸Ｎａと黒鉛とを混合する際の添加量を２００ｇにしたこと以外は、実施例１と同様に行った。 The amount of the polymer added to the graphite was the same as that of Example 1 except that the amount added when mixing the polyvinyl sulfonate Na and the graphite was 200 g so that the polymer solid content ratio was 2% by mass. It was.
炭素への処理をＣＶＤでＷＯ3を１００ｎｍつけたこと以外は、実施例１と同様に行った。The treatment for carbon was performed in the same manner as in Example 1 except that WO 3 was deposited to 100 nm by CVD.
（比較例１）
炭素への処理を行わなかったこと以外は実施例１と同様に行った。(Comparative Example 1)
The same procedure as in Example 1 was performed except that the treatment to carbon was not performed.
（比較例２）
ポリスビニルスルホン酸Ｎａの水溶液濃度を１０質量％にし、黒鉛と混合する際の添加量を１０ｇにしたこと以外は、実施例１と同様に行った。(Comparative Example 2)
This was carried out in the same manner as in Example 1 except that the concentration of the aqueous solution of sodium polyvinyl sulfonate was 10% by mass and the amount added when mixing with graphite was 10 g.
（比較例３）
ポリスビニルスルホン酸Ｎａの水溶液濃度を４．０質量％にし、黒鉛と混合する際の添加量を５０ｇにしたこと以外は、実施例１と同様に行った。(Comparative Example 3)
This was carried out in the same manner as in Example 1 except that the concentration of the aqueous solution of sodium polyvinyl sulfonate was 4.0% by mass and the addition amount when mixing with graphite was 50 g.
（比較例４）
ポリスビニルスルホン酸Ｎａの水溶液濃度を５．０質量％にし、黒鉛と混合する際の添加量を２０ｇにしたこと以外は、実施例１と同様に行った。(Comparative Example 4)
This was performed in the same manner as in Example 1 except that the concentration of the aqueous solution of sodium polyvinyl sulfonate was 5.0% by mass and the addition amount when mixing with graphite was 20 g.
（比較例５）
ポリマーをポリビニルアルコールに変更したこと意外は、実施例１と同様に行った。(Comparative Example 5)
The same procedure as in Example 1 was performed except that the polymer was changed to polyvinyl alcohol.
表１の実施例１−６と比較例１−４より、密度２．０ｇ／ｃｃにおける体積抵抗率が０．３２Ω・ｃｍ未満であるときは、圧潰試験の際に４．１Ｖおよび４．３Ｖで発煙や発火が見られたのに対し、密度２．０ｇ／ｃｃにおける体積抵抗率が０．３２Ω・ｃｍ以上では、圧潰試験の際に４．１Ｖおよび４．３Ｖで発火が見られなかったことから信頼性が向上していることは明らかである。また，実施例１−６と比較例５を比較すると，密度２．０ｇ／ｃｃにおける体積抵抗率が０．３２Ω・ｃｍ以上であっても、低密度から高密度へ変化した際の体積抵抗率の減少が大きい場合、ＤＣＲが急激に上昇し、出力密度が低下した。 From Example 1-6 of Table 1 and Comparative Example 1-4, when the volume resistivity at a density of 2.0 g / cc is less than 0.32 Ω · cm, 4.1 V and 4.3 V were used in the crushing test. Smoke and ignition were observed in the test, but when the volume resistivity at a density of 2.0 g / cc was 0.32 Ω · cm or more, no ignition was observed at 4.1 V and 4.3 V in the crush test. It is clear that the reliability has been improved. Further, comparing Example 1-6 with Comparative Example 5, even when the volume resistivity at a density of 2.0 g / cc is 0.32 Ω · cm or more, the volume resistivity when changing from low density to high density is shown. When the decrease in DCR was large, the DCR increased rapidly and the output density decreased.
このように，本発明で提供したリチウムイオン二次電池は従来技術と比較して，電池抵抗の上昇を最小限にしつつ、サイクル劣化後の電池の信頼性が向上したリチウムイオン二次電池であることが確認された。
As described above, the lithium ion secondary battery provided in the present invention is a lithium ion secondary battery in which the battery reliability after cycle deterioration is improved while minimizing the increase in battery resistance as compared with the prior art. It was confirmed.
１０ 正極
１１ セパレータ
１２ 負極
１３ 電池缶
１４ 正極タブ
１５ 負極タブ
１６ 内蓋
１７ 内圧開放弁
１８ ガスケット
１９ ＰＴＣ素子
２０ 電池蓋
２１ 軸芯DESCRIPTION OF
Claims (12)
前記負極活物質は、炭素よりなる核材を有し、密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・ｃｍ以上で、かつ式（１）を満たし、
前記炭素は、Ｘ線回折装置測定により求められる炭素００２面の面間隔が０．３３４ｎｍ以上０．３３８ｎｍ以下であることを特徴とするリチウムイオン二次電池負極活物質。
式（１）： ｒ2≧０．１３× ｒ1
式（１）において、ｒ2は、密度２．０ｇ／ｃｃにおける体積抵抗率、ｒ1は、密度１．２ｇ／ｃｃにおける体積抵抗率を表す。A negative electrode active material for lithium ion secondary batteries that absorbs and releases lithium ions,
The negative electrode active material has a core material made of carbon, the volume resistivity at a density of 2.0 g / cc is 0.32 Ω · cm or more, and satisfies the formula (1),
The lithium is a negative electrode active material for a lithium ion secondary battery, wherein the carbon has a carbon 002 plane spacing of 0.334 nm or more and 0.338 nm or less determined by X-ray diffractometer measurement.
Formula (1): r 2 ≧ 0.13 × r 1
In formula (1), r 2 represents the volume resistivity at a density of 2.0 g / cc, and r 1 represents the volume resistivity at a density of 1.2 g / cc.
前記負極活物質は、前記核材を被覆する被覆層を備えることを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to claim 1,
The negative active material for a lithium ion secondary battery, wherein the negative active material includes a coating layer that covers the core material.
前記被覆層は、ポリマーを有することを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to claim 2,
The said coating layer has a polymer, The negative electrode active material for lithium ion secondary batteries characterized by the above-mentioned.
前記ポリマーは、スルホン酸基、スルホニル基、チオール基、スルフィド基の少なくともいずれかの官能基を有することを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to claim 3,
The negative electrode active material for a lithium ion secondary battery, wherein the polymer has a functional group of at least one of a sulfonic acid group, a sulfonyl group, a thiol group, and a sulfide group.
前記ポリマーは、ビニル基、スチレン基の少なくともいずれかを有するモノマーの重合体であることを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to claim 4,
The negative electrode active material for a lithium ion secondary battery, wherein the polymer is a polymer of a monomer having at least one of a vinyl group and a styrene group.
前記ポリマーはポリビニルスルホン酸ナトリウムであることを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to claim 3,
The negative electrode active material for a lithium ion secondary battery, wherein the polymer is sodium polyvinyl sulfonate.
前記負極活物質の粒径が３μｍ以上３０μｍ以下であることを特徴とするリチウムイオン二次電池用負極活物質。The negative electrode active material for a lithium ion secondary battery according to any one of claims 1 to 6,
A negative electrode active material for a lithium ion secondary battery, wherein a particle diameter of the negative electrode active material is 3 μm or more and 30 μm or less.
前記負極活物質は、炭素よりなる核材と前記核材を被覆する被覆層とを有し、密度２．０ｇ／ｃｃにおける体積抵抗率が、０．３２Ω・ｃｍ以上で、式（１）を満たし、
前記炭素は、Ｘ線回折装置（ＸＲＤ）測定により求められる炭素００２面の面間隔が０．３３４ｎｍ以上０．３３８ｎｍ以下であり、
前記被覆層は、ポリマーを有し、
前記核材に前記ポリマーを添加する際の前記ポリマーの水溶液の濃度が０．５質量％以上２．０質量％以下であることを特徴とするリチウムイオン二次電池用負極活物質の製造方法。
式（１）： ｒ2≧０．１３× ｒ1
式（１）において、ｒ2は、密度２．０ｇ／ｃｃにおける体積抵抗率、ｒ1は、密度１．２ｇ／ｃｃにおける体積抵抗率を表す。A method for producing a negative electrode active material for a lithium ion secondary battery that occludes and releases lithium ions,
The negative electrode active material has a core material made of carbon and a coating layer that covers the core material, and the volume resistivity at a density of 2.0 g / cc is 0.32 Ω · cm or more. Meet,
The carbon has an interplanar spacing of the carbon 002 plane determined by X-ray diffractometer (XRD) measurement of 0.334 nm to 0.338 nm,
The coating layer comprises a polymer;
The method for producing a negative electrode active material for a lithium ion secondary battery, wherein the concentration of the aqueous solution of the polymer when the polymer is added to the core material is 0.5% by mass or more and 2.0% by mass or less.
Formula (1): r 2 ≧ 0.13 × r 1
In formula (1), r 2 represents the volume resistivity at a density of 2.0 g / cc, and r 1 represents the volume resistivity at a density of 1.2 g / cc.
濃度が０．５質量％以上２．０質量％以下である前記ポリマーの水溶液を調製する工程と、
前記核材に、前記ポリマーの水溶液を添加する工程と、
前記核材を含むポリマー水溶液を、８０℃以下で乾燥させる工程と、を含むリチウムイオン二次電池用負極活物質の製造方法。In the manufacturing method of the negative electrode active material for lithium ion secondary batteries in any one of Claim 3 thru | or 7,
Preparing an aqueous solution of the polymer having a concentration of 0.5% by mass or more and 2.0% by mass or less;
Adding an aqueous solution of the polymer to the core material;
Drying the polymer aqueous solution containing the core material at 80 ° C. or lower, and a method for producing a negative electrode active material for a lithium ion secondary battery.
前記負極は負極活物質、負極集電体、バインダを有し、
前記バインダは水溶性であることを特徴とするリチウムイオン二次電池用負極。The negative electrode for a lithium ion secondary battery according to claim 10,
The negative electrode has a negative electrode active material, a negative electrode current collector, a binder,
The binder is a water-soluble negative electrode for a lithium ion secondary battery.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2013/051694 WO2014115322A1 (en) | 2013-01-28 | 2013-01-28 | Negative electrode active material for lithium ion secondary cell, and lithium ion secondary cell obtained using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP5941999B2 JP5941999B2 (en) | 2016-06-29 |
| JPWO2014115322A1 true JPWO2014115322A1 (en) | 2017-01-26 |
Family
ID=51227136
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014558401A Expired - Fee Related JP5941999B2 (en) | 2013-01-28 | 2013-01-28 | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using them |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5941999B2 (en) |
| WO (1) | WO2014115322A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7099489B2 (en) * | 2020-04-10 | 2022-07-12 | 三菱マテリアル株式会社 | Negative electrode material, battery, method of manufacturing negative electrode material, and method of manufacturing battery |
| CN115020671B (en) * | 2022-06-29 | 2023-10-24 | 蜂巢能源科技股份有限公司 | Lithium iron phosphate-based composite material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4524818B2 (en) * | 1999-10-05 | 2010-08-18 | 三菱化学株式会社 | Negative electrode material for lithium ion battery and lithium ion secondary battery using the same |
| JP5469979B2 (en) * | 2009-09-30 | 2014-04-16 | 日立ビークルエナジー株式会社 | Lithium ion secondary battery |
| JP5540805B2 (en) * | 2010-03-23 | 2014-07-02 | 三菱化学株式会社 | Non-aqueous secondary battery carbon material, negative electrode material and non-aqueous secondary battery |
| JP5961922B2 (en) * | 2010-05-31 | 2016-08-03 | 日産自動車株式会社 | Negative electrode for secondary battery and method for producing the same |
-
2013
- 2013-01-28 WO PCT/JP2013/051694 patent/WO2014115322A1/en active Application Filing
- 2013-01-28 JP JP2014558401A patent/JP5941999B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014115322A1 (en) | 2014-07-31 |
| JP5941999B2 (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6181590B2 (en) | Anode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery | |
| JP5986836B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, lithium ion secondary battery, and production method thereof | |
| WO2017217408A1 (en) | Lithium ion secondary cell | |
| JP6494194B2 (en) | Coated positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery using the same | |
| TW201330350A (en) | Lithium battery | |
| JP2016058187A (en) | Nonaqueous electrolyte secondary battery | |
| CN107660316B (en) | Positive electrode of lithium electrochemical power generation device | |
| JP2011090876A (en) | Lithium secondary battery and method of manufacturing the same | |
| WO2015001871A1 (en) | Nonaqueous electrolyte secondary cell and method for producing same | |
| WO2014148043A1 (en) | Nonaqueous electrolyte secondary battery | |
| WO2012111545A1 (en) | Non-aqueous electrolyte secondary battery | |
| JP6448462B2 (en) | Anode active material for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and method for producing anode active material for nonaqueous electrolyte secondary battery | |
| JP2007250390A (en) | Negative electrode, secondary battery and manufacturing method of negative electrode | |
| JP5855737B2 (en) | Lithium ion battery | |
| JP6413833B2 (en) | Negative electrode active material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP6272996B2 (en) | Negative electrode material, negative electrode for lithium ion secondary battery, lithium ion secondary battery, and production method thereof | |
| WO2011058979A1 (en) | Lithium secondary battery | |
| JP4513385B2 (en) | Negative electrode for secondary battery and secondary battery | |
| JP5843107B2 (en) | Method for producing non-aqueous electrolyte secondary battery | |
| US10340514B2 (en) | Negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP6627708B2 (en) | Lithium ion secondary battery and method of manufacturing lithium ion secondary battery | |
| JP2015204178A (en) | Negative electrode for lithium ion secondary batteries, lithium ion secondary battery, and manufacturing methods thereof | |
| JP5941999B2 (en) | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery using them | |
| JP2012084554A (en) | Anode, secondary battery, and method for manufacturing anode | |
| JP5920666B2 (en) | Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160329 |
|
| 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: 20160426 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160523 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5941999 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| LAPS | Cancellation because of no payment of annual fees |