JP6938914B2 - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery - Google Patents
Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery Download PDFInfo
- Publication number
- JP6938914B2 JP6938914B2 JP2017000169A JP2017000169A JP6938914B2 JP 6938914 B2 JP6938914 B2 JP 6938914B2 JP 2017000169 A JP2017000169 A JP 2017000169A JP 2017000169 A JP2017000169 A JP 2017000169A JP 6938914 B2 JP6938914 B2 JP 6938914B2
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- ion secondary
- secondary battery
- lithium ion
- electrode material
- 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.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 103
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 103
- 239000007773 negative electrode material Substances 0.000 title claims description 103
- 239000011856 silicon-based particle Substances 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 27
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000002429 nitrogen sorption measurement Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 31
- 239000002002 slurry Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 239000010703 silicon Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- -1 O 8 Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-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
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- LBKMJZAKWQTTHC-UHFFFAOYSA-N 4-methyldioxolane Chemical compound CC1COOC1 LBKMJZAKWQTTHC-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 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
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010090 LiAlO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013131 LiN Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-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
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011320 asphalt decomposition pitch Substances 0.000 description 1
- DISYGAAFCMVRKW-UHFFFAOYSA-N butyl ethyl carbonate Chemical compound CCCCOC(=O)OCC DISYGAAFCMVRKW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FWBMVXOCTXTBAD-UHFFFAOYSA-N butyl methyl carbonate Chemical compound CCCCOC(=O)OC FWBMVXOCTXTBAD-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011319 crude-oil pitch Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000014786 phosphorus Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011318 synthetic pitch Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明はリチウムイオン二次電池用負極材、リチウムイオン二次電池用負極及びリチウムイオン二次電池に関する。 The present invention relates to a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
リチウムイオン二次電池用負極材には、リチウムイオンを吸蔵放出する炭素材料が広く使用されている。炭素材料としては、黒鉛が挙げられる。黒鉛を炭素材料として用いると、充放電におけるリチウムイオンの吸蔵放出反応が可逆性に優れるため、サイクル特性が良好なリチウムイオン二次電池が得られる。しかしながら、黒鉛のリチウムイオンの吸蔵放出容量は、ＬｉＣ６を形成した場合の３７２ｍＡｈ／ｇが理論値であり、さらなる高容量化には限界がある。 A carbon material that occludes and releases lithium ions is widely used as a negative electrode material for a lithium ion secondary battery. Examples of the carbon material include graphite. When graphite is used as the carbon material, the lithium ion occlusion / discharge reaction during charge / discharge is excellent in reversibility, so that a lithium ion secondary battery having good cycle characteristics can be obtained. However, the occlusal / releasing capacity of lithium ions in graphite is 372 mAh / g when LiC 6 is formed as a theoretical value, and there is a limit to further increasing the capacity.
シリコン（Ｓｉ）は、リチウムと合金（金属間化合物）を形成するため、電気化学的にリチウムイオンを吸蔵放出することが可能である。リチウムイオンの吸蔵放出容量は、Ｌｉ２２Ｓｉ５を形成した場合の４１９７ｍＡｈ／ｇが理論値であり、黒鉛負極よりも高容量化することが可能である。 Since silicon (Si) forms an alloy (intermetallic compound) with lithium, it is possible to electrochemically occlude and release lithium ions. The theoretical value of the occlusal / releasing capacity of lithium ions is 4197 mAh / g when Li 22 Si 5 is formed, and the capacity can be made higher than that of the graphite negative electrode.
一方で、シリコンはリチウムイオンの吸蔵放出にともない３倍〜４倍の大きな体積変化を生じる。このため、充放電サイクルを行った場合、膨張収縮が繰り返されることによりシリコンが崩壊して微細化してしまい、良好なサイクル寿命が得られないという課題があった。そこで、黒鉛粒子、シリコン微粒子及び非晶質炭素を含む複合粒子の表面に、黒鉛又はカーボンブラックから選ばれる少なくとも１種類以上の物質である炭素質物質が配置されるとともに、該炭素質物質が非晶質炭素によって被覆された構造を有するリチウムイオン二次電池材料が開示されている（例えば、特許文献１参照）。 On the other hand, silicon causes a large volume change of 3 to 4 times with the occlusion and release of lithium ions. For this reason, when the charge / discharge cycle is performed, there is a problem that silicon collapses and becomes finer due to repeated expansion and contraction, and a good cycle life cannot be obtained. Therefore, a carbonaceous substance, which is at least one kind of substance selected from graphite or carbon black, is arranged on the surface of composite particles containing graphite particles, silicon fine particles, and amorphous carbon, and the carbonaceous substance is not present. A lithium ion secondary battery material having a structure coated with crystalline carbon is disclosed (see, for example, Patent Document 1).
リチウムイオン二次電池の高容量化に対する要求が高まっているなか、さらに高容量であるリチウムイオン二次電池を作製可能な負極材が求められている。そこで本発明は、高容量であるリチウムイオン二次電池を作製可能なリチウムイオン二次電池用負極材、ならびにこれを用いたリチウムイオン二次電池用負極及びリチウムイオン二次電池を提供することを課題とする。 As the demand for higher capacity lithium ion secondary batteries is increasing, there is a demand for a negative electrode material capable of producing a lithium ion secondary battery having a higher capacity. Therefore, the present invention provides a negative electrode material for a lithium ion secondary battery capable of producing a lithium ion secondary battery having a high capacity, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same. Make it an issue.
上記課題を解決するための手段は、以下の通りである。 The means for solving the above problems are as follows.
＜１＞ アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子であるリチウムイオン二次電池用負極材。
＜２＞ アスペクト比が１〜２０、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子と、前記シリコン粒子の表面上の少なくとも一部に形成された炭素層と、を備えるリチウムイオン二次電池用負極材。
＜３＞ 前記シリコン粒子に対する前記炭素層の質量比が、０．００１〜０．３である、＜２＞に記載のリチウムイオン二次電池用負極材。
＜４＞ Ｒ値が、０．５〜２．５である＜２＞又は＜３＞に記載のリチウムイオン二次電池用負極材。
＜５＞ 体積平均粒子径（Ｄ５０）が０．５μｍ〜２０μｍである＜１＞〜＜４＞のいずれか１つに記載のリチウムイオン二次電池用負極材。
＜６＞ ７７Ｋでの窒素吸着測定より求めた比表面積が０．５ｍ２／ｇ〜３０ｍ２／ｇである＜１＞〜＜５＞のいずれか１つに記載のリチウムイオン二次電池用負極材。
<1> A negative electrode material for a lithium ion secondary battery, which is a flat silicon particle having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less.
<2> A lithium ion secondary battery including flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less, and a carbon layer formed on at least a part of the surface of the silicon particles. Negative electrode material for.
<3> The negative electrode material for a lithium ion secondary battery according to <2>, wherein the mass ratio of the carbon layer to the silicon particles is 0.001 to 0.3.
<4> The negative electrode material for a lithium ion secondary battery according to <2> or <3>, which has an R value of 0.5 to 2.5.
<5> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <4>, which has a volume average particle diameter (D 50) of 0.5 μm to 20 μm.
<6> The specific surface area determined from nitrogen adsorption measurements at 77K is 0.5m 2 / g~30m 2 / g < 1> ~ <5> The negative electrode for a lithium ion secondary battery according to any one of Material.
＜７＞ ＜１＞〜＜６＞のいずれか１つに記載のリチウムイオン二次電池用負極材を含む、リチウムイオン二次電池用負極。 <7> A negative electrode for a lithium ion secondary battery, which comprises the negative electrode material for a lithium ion secondary battery according to any one of <1> to <6>.
＜８＞ ＜７＞に記載のリチウムイオン二次電池用負極と、正極と、電解質とを含むリチウムイオン二次電池。 <8> The lithium ion secondary battery including the negative electrode for the lithium ion secondary battery, the positive electrode, and the electrolyte according to <7>.
本発明によれば、高容量であるリチウムイオン二次電池を作製可能なリチウムイオン二次電池用負極材、ならびにこれを用いたリチウムイオン二次電池用負極及びリチウムイオン二次電池が提供される。 According to the present invention, there is provided a negative electrode material for a lithium ion secondary battery capable of producing a lithium ion secondary battery having a high capacity, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same. ..
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。また、本明細書に開示される技術的思想の範囲内において、様々な変更及び修正が可能である。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention. In addition, various changes and amendments are possible within the scope of the technical ideas disclosed herein.
本明細書において「工程」との語には、他の工程から独立した工程に加え、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目的が達成されれば、当該工程も含まれる。
本明細書において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書においてスラリー中の各成分の含有量は、スラリー中に各成分に該当する物質が複数種存在する場合、特に断らない限り、スラリー中に存在する当該複数種の物質の合計の含有量を意味する。
本明細書において「層」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。
本明細書において各成分の粒子径は、各成分に該当する粒子が複数種存在する場合、特に断らない限り、当該複数種の粒子の混合物についての値を意味する。
In the present specification, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. Is done.
In the numerical range indicated by using "~" in the present specification, the numerical values before and after "~" are included as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present specification, the content of each component in the slurry is the total content of the plurality of substances present in the slurry when a plurality of substances corresponding to each component are present in the slurry, unless otherwise specified. Means.
In the present specification, the term "layer" includes not only the configuration of the shape formed on the entire surface but also the configuration of the shape formed in a part when observed as a plan view.
In the present specification, the particle size of each component means a value for a mixture of the plurality of types of particles when a plurality of types of particles corresponding to each component are present, unless otherwise specified.
［第１実施形態］
＜リチウムイオン二次電池用負極材＞
第１実施形態のリチウムイオン二次電池用負極材（以下、単に負極材とも称する）は、アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子である。このような負極材は、黒鉛粒子を用いる従来の負極材と比較して高容量であるリチウムイオン二次電池を作製可能である。さらに、このような負極材は、シリコン粒子を用いる従来の負極材と比較して高効率かつ高寿命であるリチウムイオン二次電池を作製可能である。また、このようなシリコン粒子としては、鱗状、鱗片状、一部塊状等の形状を有するものが挙げられる。
[First Embodiment]
<Negative electrode material for lithium-ion secondary batteries>
The negative electrode material for a lithium ion secondary battery of the first embodiment (hereinafter, also simply referred to as a negative electrode material) is flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less. Such a negative electrode material can produce a lithium ion secondary battery having a higher capacity than a conventional negative electrode material using graphite particles. Further, such a negative electrode material can produce a lithium ion secondary battery having high efficiency and long life as compared with a conventional negative electrode material using silicon particles. Moreover, examples of such silicon particles include those having a shape such as a scale-like shape, a scale-like shape, and a partially lump-like shape.
シリコン粒子は、長軸方向の長さをＡ、短軸方向の長さをＢとしたときに、Ａ／Ｂで表されるアスペクト比が１〜２０であり、３〜１５であってもよく、５〜１０であってもよい。アスペクト比が１以上であることにより、粒子間の接触面積が増加して、導電性がより向上する傾向にあり、アスペクト比が２０以下であることにより、充放電サイクルを行う際のシリコンの崩壊が抑制され、リチウムイオン二次電池が長寿命となる傾向にある。 When the length in the major axis direction is A and the length in the minor axis direction is B, the silicon particles have an aspect ratio of 1 to 20 represented by A / B, and may be 3 to 15. It may be 5 to 10. When the aspect ratio is 1 or more, the contact area between the particles tends to increase and the conductivity tends to be further improved, and when the aspect ratio is 20 or less, the decay of silicon during the charge / discharge cycle is performed. Is suppressed, and the lithium ion secondary battery tends to have a long life.
シリコン粒子のアスペクト比は、図１に示すように、シリコン粒子の長軸方向の長さをＡ、短軸方向の長さをＢとしたとき、Ａ／Ｂで表される。本明細書において、アスペクト比は、顕微鏡でシリコン粒子を拡大し、任意に１０個のシリコン粒子を選択してＡ／Ｂを測定して、その測定値の算術平均値をとったものである。なお、図１は、本実施形態に係るリチウムイオン二次電池用負極材である扁平なシリコン粒子を示す概略図であり、ＡとＢ及びＢ’、ならびにＡ’とＢ及びＢ’とはそれぞれ直交している。
ここで、長軸方向の長さは、観察されるシリコン粒子を二本の平行線Ａ、Ａ’で接するように挟んだとき、その間隔が最も大きくなる場合のＡ、Ａ’間の距離であり、短軸方向の長さは、前記長軸方向の長さを決める二本の平行線Ａ、Ａ’に対して垂直な二本の平行線Ｂ、Ｂ’で前記シリコン粒子を接するよう挟んだときのそのＢ、Ｂ’間の距離である。なお、シリコン粒子の短軸方向の長さは、シリコン粒子の厚みよりも長く、０．５μｍ以上となる。
As shown in FIG. 1, the aspect ratio of the silicon particles is represented by A / B, where A is the length in the major axis direction and B is the length in the minor axis direction of the silicon particles. In the present specification, the aspect ratio is obtained by magnifying silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring A / B, and taking an arithmetic mean value of the measured values. Note that FIG. 1 is a schematic view showing flat silicon particles which are negative electrode materials for a lithium ion secondary battery according to the present embodiment, and A, B and B', and A', B and B', respectively. It is orthogonal.
Here, the length in the major axis direction is the distance between A and A'when the observed silicon particles are sandwiched so as to be in contact with two parallel lines A and A', and the interval is the largest. Yes, the length in the minor axis direction is sandwiched so that the silicon particles are in contact with the two parallel lines B, B'that are perpendicular to the two parallel lines A, A'that determine the length in the major axis direction. It is the distance between B and B'at that time. The length of the silicon particles in the minor axis direction is longer than the thickness of the silicon particles and is 0.5 μm or more.
さらに、シリコン粒子の厚みは、０．５μｍ以下であり、好ましくは０．０１μｍ〜０．４μｍであり、より好ましくは０．０５μｍ〜０．３μｍ以下である。シリコン粒子の厚みが０．５μｍ以下であることにより、充放電サイクルを行う際のシリコンの崩壊が抑制され、リチウムイオン二次電池が長寿命となる傾向にある。 Further, the thickness of the silicon particles is 0.5 μm or less, preferably 0.01 μm to 0.4 μm, and more preferably 0.05 μm to 0.3 μm or less. When the thickness of the silicon particles is 0.5 μm or less, the decay of silicon during the charge / discharge cycle is suppressed, and the lithium ion secondary battery tends to have a long life.
シリコン粒子の厚みは、シリコン粒子を顕微鏡で観察し、任意に１０個のシリコン粒子を選択して厚みを測定して、その測定値の算術平均値をとったものである。
ここで、シリコン粒子の厚みは、長軸方向及び短軸方向に直交する方向において、観察されるシリコン粒子を二本の平行線Ｃ、Ｃ’で接するように挟んだとき、その間隔が最も大きくなる場合のＣ、Ｃ’間の距離である。
The thickness of the silicon particles is obtained by observing the silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring the thickness, and taking the arithmetic mean value of the measured values.
Here, the thickness of the silicon particles is the largest when the observed silicon particles are sandwiched by two parallel lines C and C'in the directions orthogonal to the major axis direction and the minor axis direction. It is the distance between C and C'when it becomes.
負極材の体積平均粒子径（Ｄ５０）は、０．５μｍ〜２０μｍであることが好ましく、０．６μｍ〜１０μｍであることがより好ましく、０．７μｍ〜５μｍであることが更に好ましい。負極材の体積平均粒子径が０．５μｍ以上であると、充分なタップ密度と、負極材スラリーとしたときの良好な塗工性が得られる傾向にある。一方、負極材の体積平均粒子径が２０μｍ以下であると、負極材の表面から内部へのリチウムの拡散距離が長くなりすぎず、リチウムイオン二次電池の入出力特性が良好に維持される傾向にある。 The volume average particle diameter (D 50 ) of the negative electrode material is preferably 0.5 μm to 20 μm, more preferably 0.6 μm to 10 μm, and even more preferably 0.7 μm to 5 μm. When the volume average particle size of the negative electrode material is 0.5 μm or more, a sufficient tap density and good coatability when the negative electrode material slurry is obtained tend to be obtained. On the other hand, when the volume average particle diameter of the negative electrode material is 20 μm or less, the diffusion distance of lithium from the surface of the negative electrode material to the inside does not become too long, and the input / output characteristics of the lithium ion secondary battery tend to be well maintained. It is in.
負極材の体積平均粒子径（Ｄ５０）は、負極材の粒子径分布において、小径側から体積累積分布曲線を描いた場合に、累積５０％となるときの粒子径である。体積平均粒子径（Ｄ５０）は、例えば、精製水に界面活性剤とともに負極材を分散させ、レーザー回折式粒度分布測定装置（例えば、株式会社島津製作所製、ＳＡＬＤ−３０００Ｊ）で測定することができる。 The volume average particle size (D 50 ) of the negative electrode material is the particle size when the cumulative volume is 50% when the volume cumulative distribution curve is drawn from the small diameter side in the particle size distribution of the negative electrode material. The volume average particle size (D 50 ) can be measured, for example, by dispersing a negative electrode material together with a surfactant in purified water and using a laser diffraction type particle size distribution measuring device (for example, SALD-3000J manufactured by Shimadzu Corporation). can.
負極材の７７Ｋでの窒素吸着測定より求められる比表面積（以下、Ｎ２比表面積とも称する）は、０．５ｍ２／ｇ〜３０ｍ２／ｇであることが好ましく、５ｍ２／ｇ〜２５ｍ２／ｇであることがより好ましく、１０ｍ２／ｇ〜２５ｍ２／ｇであることが更に好ましい。Ｎ２比表面積が上記範囲内であれば、入出力特性と初回充放電効率の良好なバランスが得られる傾向にある。Ｎ２比表面積は、具体的には、後述する実施例の方法により求めることができる。 Specific surface area determined from nitrogen adsorption measurements at 77K of negative electrode material (hereinafter, also referred to as N 2 specific surface area) is preferably 0.5m 2 / g~30m 2 / g, 5m 2 / g~25m 2 more preferably / is g, more preferably 10m 2 / g~25m 2 / g. When the N 2 specific surface area is within the above range, a good balance between input / output characteristics and initial charge / discharge efficiency tends to be obtained. Specifically, the N 2 specific surface area can be determined by the method of Examples described later.
アスペクト比が１〜２０であり、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子としては、例えば、純シリコンを機械的研磨した際に発生したシリコン粉が挙げられる。 Examples of the flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less include silicon powder generated when pure silicon is mechanically polished.
［第２実施形態］
＜リチウムイオン二次電池用負極材＞
第２実施形態のリチウムイオン二次電池用負極材（以下、単に負極材とも称する）は、アスペクト比が１〜２０、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子と、シリコン粒子の表面上の少なくとも一部に形成された炭素層と、を備える。第２実施形態の負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されている点で、第１実施形態の負極材と相違する。
[Second Embodiment]
<Negative electrode material for lithium-ion secondary batteries>
The negative electrode material for a lithium ion secondary battery of the second embodiment (hereinafter, also simply referred to as a negative electrode material) includes flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less, and the surface of the silicon particles. It comprises a carbon layer formed in at least a part of the above. The negative electrode material of the second embodiment is different from the negative electrode material of the first embodiment in that a carbon layer is formed on at least a part of the surface of the silicon particles.
さらに、負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されているため、比表面積を下げ、ＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｐｈａｓｅ）膜の生成量を下げることができる傾向にある。なお、ＳＥＩ膜が生成されると電池の初期特性（例えば、充放電効率）の低下につながる。
また、シリコン粒子の表面上の少なくとも一部に炭素層が形成されていることにより、シリコン粒子と、シリコンと反応性が高い電解液との接触が抑制され、電解液の分解が抑制される傾向にある。これにより、初期特性低下が抑制される傾向にある。
また、シリコン粒子の表面上の少なくとも一部に炭素層を形成させて導電性を付与することにより、粒子表面の導電性が向上し、かつリチウムの吸蔵及び放出に伴う体積変化に対して安定な構造となる傾向にある。その結果として、リチウムイオン二次電池における長期安定性及び初期効率が改善される傾向にある。
なお、負極材は、シリコン粒子の表面上の少なくとも一部に炭素層が形成されていればよく、シリコン粒子の表面の一部に炭素層が形成されていてもよく、シリコン粒子の表面の全部に炭素層が形成されていてもよい。
Further, since the negative electrode material has a carbon layer formed on at least a part of the surface of the silicon particles, there is a tendency that the specific surface area can be lowered and the amount of SEI (Solid Electrolyte Interphase) film formed can be reduced. When the SEI film is formed, the initial characteristics of the battery (for example, charge / discharge efficiency) are lowered.
Further, since the carbon layer is formed on at least a part of the surface of the silicon particles, the contact between the silicon particles and the electrolytic solution having high reactivity with silicon is suppressed, and the decomposition of the electrolytic solution tends to be suppressed. It is in. As a result, the deterioration of the initial characteristics tends to be suppressed.
Further, by forming a carbon layer on at least a part of the surface of the silicon particles to impart conductivity, the conductivity of the particle surface is improved and stable against volume changes due to occlusion and release of lithium. It tends to be a structure. As a result, the long-term stability and initial efficiency of lithium-ion secondary batteries tend to be improved.
The negative electrode material may have a carbon layer formed on at least a part of the surface of the silicon particles, or may have a carbon layer formed on a part of the surface of the silicon particles, and the entire surface of the silicon particles may be formed. A carbon layer may be formed on the surface.
シリコン粒子に対する炭素層の質量比は０．００１〜０．３であることが好ましく、０．００２〜０．２５であることがより好ましく、０．００５〜０．２であることが更に好ましい。炭素層の質量比が０．００１以上であることにより、炭素層を設けたことによる前述の効果をより好適に奏する傾向にあり、炭素層の質量比が０．３以下であることにより、シリコン割合の低下を抑制してより高容量のリチウムイオン二次電池とすることができる傾向にある。 The mass ratio of the carbon layer to the silicon particles is preferably 0.001 to 0.3, more preferably 0.002 to 0.25, and even more preferably 0.005 to 0.2. When the mass ratio of the carbon layer is 0.001 or more, the above-mentioned effect due to the provision of the carbon layer tends to be more preferably exhibited, and when the mass ratio of the carbon layer is 0.3 or less, silicon. There is a tendency that a lithium ion secondary battery having a higher capacity can be obtained by suppressing a decrease in the ratio.
シリコン粒子の表面上の少なくとも一部に炭素層を形成する方法は、特に限定されない。例えば、以下のような湿式混合方式、乾式混合方式、気相方式等の方法が挙げられる。 The method of forming a carbon layer on at least a part of the surface of the silicon particles is not particularly limited. For example, the following methods such as a wet mixing method, a dry mixing method, and a gas phase method can be mentioned.
湿式混合方式の方法としては、炭素層を構成する炭素質材料又はその前駆体となる物質（有機化合物等）を溶媒に溶解又は分散させた混合液に、シリコン粒子を分散して混合した後、溶媒を除去する方法が挙げられる。前駆体を用いた場合、前駆体を付着させた状態のシリコン粒子を熱処理して前駆体を炭素化することにより、シリコン粒子を炭素質材料で被覆することができる。 As a wet mixing method, silicon particles are dispersed and mixed in a mixed solution in which a carbonaceous material constituting a carbon layer or a substance (organic compound or the like) which is a precursor thereof is dissolved or dispersed in a solvent, and then mixed. A method of removing the solvent can be mentioned. When a precursor is used, the silicon particles can be coated with a carbonaceous material by heat-treating the silicon particles with the precursor attached to carbonize the precursor.
乾式混合方式の方法としては、シリコン粒子と有機化合物とをそれぞれ固体の状態で混合し、得られた混合物に力学的エネルギーを加えることでシリコン粒子の表面に有機化合物を付着させ、有機化合物を付着させた状態のシリコン粒子を熱処理して有機化合物を炭素化することにより、シリコン粒子を炭素質材料で被覆することができる。 As a dry mixing method, the silicon particles and the organic compound are mixed in a solid state, and the organic compound is attached to the surface of the silicon particles by applying mechanical energy to the obtained mixture, and the organic compound is attached. By heat-treating the silicon particles in the state of being made to carbonize the organic compound, the silicon particles can be coated with a carbonaceous material.
気相方式の方法としては、ＣＶＤ法等の、アセチレン、プロピレン等のガス分解反応によってシリコン粒子の表面を炭素質材料で被覆する方法が挙げられる。 Examples of the vapor phase method include a method of coating the surface of silicon particles with a carbonaceous material by a gas decomposition reaction of acetylene, propylene or the like, such as a CVD method.
有機化合物の具体例としては、エチレンヘビーエンドピッチ、原油ピッチ、コールタールピッチ、アスファルト分解ピッチ、ポリ塩化ビニル等を熱分解して生成するピッチ、ナフタレン等を超強酸存在下で重合させて作製される合成ピッチなどが挙げられる。また、ポリ塩化ビニル、ポリビニルアルコール、ポリ酢酸ビニル、ポリビニルブチラール等の熱可塑性合成樹脂を有機化合物として用いることもできる。また、デンプン、セルロース等の天然物を有機化合物として用いることもできる。 Specific examples of organic compounds include ethylene heavy end pitch, crude oil pitch, coal tar pitch, asphalt decomposition pitch, pitch produced by thermal decomposition of polyvinyl chloride, etc., and naphthalene, etc., which are produced by polymerizing in the presence of super-strong acids. Synthetic pitch and the like. Further, a thermoplastic synthetic resin such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate and polyvinyl butyral can also be used as the organic compound. In addition, natural products such as starch and cellulose can also be used as organic compounds.
熱処理の温度は６００℃〜１１００℃であることが好ましく、６５０℃〜１０００℃であることがより好ましく、７００℃〜９００℃であることがさらに好ましい。熱処理時の雰囲気は、負極材が酸化し難い雰囲気であれば特に制限はなく、窒素ガス雰囲気、アルゴンガス雰囲気、自己分解ガス雰囲気等が適用できる。使用する炉の形式は特に制限はないが、電気又はガスを熱源としたバッチ炉、連続炉等が好ましい。 The temperature of the heat treatment is preferably 600 ° C. to 1100 ° C., more preferably 650 ° C. to 1000 ° C., and even more preferably 700 ° C. to 900 ° C. The atmosphere at the time of heat treatment is not particularly limited as long as the negative electrode material is difficult to oxidize, and a nitrogen gas atmosphere, an argon gas atmosphere, a self-decomposing gas atmosphere and the like can be applied. The type of furnace used is not particularly limited, but a batch furnace or a continuous furnace using electricity or gas as a heat source is preferable.
（ラマン分光測定のＲ値）
負極材のラマン分光測定のＲ値は０．５〜２．５であることが好ましく、０．７〜２．０であることがより好ましく、０．８〜１．５であることが更に好ましい。Ｒ値が０．５以上であると、リチウムイオンの挿入及び脱離に用いられる黒鉛格子欠陥が充分存在し、入出力特性の低下が抑制される傾向にある。Ｒ値が２．５以下であると、電解液の分解反応が充分に抑制され、初回効率の低下が抑制される傾向にある。
(R value of Raman spectroscopy)
The R value of the Raman spectroscopic measurement of the negative electrode material is preferably 0.5 to 2.5, more preferably 0.7 to 2.0, and even more preferably 0.8 to 1.5. .. When the R value is 0.5 or more, graphite lattice defects used for insertion and desorption of lithium ions are sufficiently present, and deterioration of input / output characteristics tends to be suppressed. When the R value is 2.5 or less, the decomposition reaction of the electrolytic solution is sufficiently suppressed, and the decrease in the initial efficiency tends to be suppressed.
Ｒ値は、ラマン分光測定において得られたラマン分光スペクトルにおいて、１５８０ｃｍ−１付近に現れるピークの強度Ｉｇと、１３６０ｃｍ−１付近に現れるピークの強度Ｉｄの強度比（Ｉｄ／Ｉｇ）と定義する。ここで、１５８０ｃｍ−１付近に現れるピークとは、通常、黒鉛結晶構造に対応すると同定されるピークであり、例えば１５３０ｃｍ−１〜１６３０ｃｍ−１に観測されるピークを意味する。また１３６０ｃｍ−１付近に現れるピークとは、通常、炭素の非晶質構造に対応すると同定されるピークであり、例えば１３００ｃｍ−１〜１４００ｃｍ−１に観測されるピークを意味する。 R value, in the Raman spectrum obtained in the Raman spectrometry, to define the intensity Ig of the peak appearing near 1580 cm -1, the intensity ratio of the intensity Id of the peak appearing near 1360 cm -1 and (Id / Ig). Here, the peak appearing near 1580 cm -1, generally a peak identified as corresponding to the graphite crystal structure, means a peak observed for example 1530cm -1 ~1630cm -1. Further a peak appearing near 1360 cm -1, generally a peak identified as corresponding to the amorphous structure of the carbon, means a peak observed for example 1300cm -1 ~1400cm -1.
本明細書においてラマン分光測定は、レーザーラマン分光光度計（日本分光株式会社製、ＮＲＳ−２１００）を用い、リチウムイオン二次電池用負極材を平らになるようにセットした試料板にアルゴンレーザー光を照射して測定を行う。測定条件は例えば以下の通りである。
レーザー出力１０ｍＷ
分光器Ｆシングル
入射スリット幅８００μｍ
積算回数３回
露光時間６０秒
In the present specification, the Raman spectroscopic measurement uses a laser Raman spectrophotometer (NRS-2100, manufactured by Nippon Spectroscopy Co., Ltd.), and argon laser light is applied to a sample plate in which the negative electrode material for a lithium ion secondary battery is set flat. Is irradiated to measure. The measurement conditions are as follows, for example.
Laser output 10mW
Spectrometer F Single Incident slit width 800 μm
Cumulative number of times 3
負極材の体積平均粒子径（Ｄ５０）は、０．５μｍ〜２０μｍであることが好ましく、０．６μｍ〜１０μｍであることがより好ましく、０．７μｍ〜５μｍであることが更に好ましい。負極材の体積平均粒子径が０．５μｍ以上であると、充分なタップ密度と、負極材スラリーとしたときの良好な塗工性が得られる傾向にある。一方、負極材の体積平均粒子径が２０μｍ以下であると、負極材の表面から内部へのリチウムの拡散距離が長くなりすぎず、リチウムイオン二次電池の入出力特性が良好に維持される傾向にある。 The volume average particle diameter (D 50 ) of the negative electrode material is preferably 0.5 μm to 20 μm, more preferably 0.6 μm to 10 μm, and even more preferably 0.7 μm to 5 μm. When the volume average particle size of the negative electrode material is 0.5 μm or more, a sufficient tap density and good coatability when the negative electrode material slurry is obtained tend to be obtained. On the other hand, when the volume average particle diameter of the negative electrode material is 20 μm or less, the diffusion distance of lithium from the surface of the negative electrode material to the inside does not become too long, and the input / output characteristics of the lithium ion secondary battery tend to be well maintained. It is in.
負極材の体積平均粒子径（Ｄ５０）は、前述の第１実施形態に記載の方法にて測定することができる。 The volume average particle diameter (D 50 ) of the negative electrode material can be measured by the method described in the first embodiment described above.
負極材の７７Ｋでの窒素吸着測定より求められる比表面積（以下、Ｎ２比表面積とも称する）は、０．５ｍ２／ｇ〜３０ｍ２／ｇであることが好ましく、５ｍ２／ｇ〜２５ｍ２／ｇであることがより好ましく、１０ｍ２／ｇ〜２５ｍ２／ｇであることが更に好ましい。Ｎ２比表面積が上記範囲内であれば、入出力特性と初回充放電効率の良好なバランスが得られる傾向にある。Ｎ２比表面積は、前述の第１実施形態に記載の方法を用いて求めることができる。 Specific surface area determined from nitrogen adsorption measurements at 77K of negative electrode material (hereinafter, also referred to as N 2 specific surface area) is preferably 0.5m 2 / g~30m 2 / g, 5m 2 / g~25m 2 more preferably / is g, more preferably 10m 2 / g~25m 2 / g. When the N 2 specific surface area is within the above range, a good balance between input / output characteristics and initial charge / discharge efficiency tends to be obtained. The N 2 specific surface area can be determined by using the method described in the first embodiment described above.
＜リチウムイオン二次電池用負極＞
本実施形態のリチウムイオン二次電池用負極（以下、単に負極とも称する）は、本実施形態のリチウムイオン二次電池用負極材を含む。これにより、高容量であるリチウムイオン二次電池を構成することが可能となる。また、リチウムイオン二次電池用負極は、リチウムイオン二次電池用負極材を含む負極層と、集電体と、を含んでいてもよい。リチウムイオン二次電池用負極は、必要に応じて他の構成要素を含んでもよい。
<Negative electrode for lithium-ion secondary battery>
The negative electrode for a lithium ion secondary battery of the present embodiment (hereinafter, also simply referred to as a negative electrode) includes the negative electrode material for a lithium ion secondary battery of the present embodiment. This makes it possible to construct a lithium ion secondary battery having a high capacity. Further, the negative electrode for a lithium ion secondary battery may include a negative electrode layer containing a negative electrode material for a lithium ion secondary battery and a current collector. The negative electrode for a lithium ion secondary battery may contain other components if necessary.
リチウムイオン二次電池用負極は、例えば、リチウムイオン二次電池用負極材及び有機系結着剤を溶剤とともに撹拌機、ボールミル、スーパーサンドミル、加圧ニーダー等の分散装置により混練し、負極材スラリーを調製し、これを集電体に塗布して負極層を形成する、又は、ペースト状の負極材スラリーをシート状、ペレット状等の形状に成形し、これを集電体と一体化することで得ることができる。 For the negative electrode for a lithium ion secondary battery, for example, the negative electrode material for a lithium ion secondary battery and an organic binder are kneaded together with a solvent by a disperser such as a stirrer, a ball mill, a super sand mill, or a pressure kneader, and the negative electrode material slurry is used. Is prepared and applied to the current collector to form a negative electrode layer, or a paste-like negative electrode material slurry is formed into a sheet or pellet shape and integrated with the current collector. Can be obtained at.
有機系結着剤としては、特に限定されず、スチレン−ブタジエン共重合体、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、（メタ）アクリロニトリル、ヒドロキシエチル（メタ）アクリレート等のエチレン性不飽和カルボン酸エステルの重合体；アクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエチレン性不飽和カルボン酸の重合体；ポリフッ化ビニリデン、ポリエチレンオキサイド、ポリエピクロヒドリン、ポリフォスファゼン、ポリアクリロニトリル等のイオン導電性の大きな高分子化合物などが挙げられる。この有機系結着剤の含有量は、リチウムイオン二次電池用負極材と有機系結着剤の合計１００質量部に対して０．５質量部〜２０質量部であることが好ましい。有機系結着剤は１種を単独で用いても、２種以上を組み合わせて用いてもよい。（メタ）アクリレートは、アクリレート又はメタクリレートを意味し、（メタ）アクリロニトリルはアクリロニトリル又はメタクリロニトリルを意味する。 The organic binder is not particularly limited, and is not particularly limited, such as a styrene-butadiene copolymer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, and hydroxyethyl (meth) acrylate. Polymers of ethylenically unsaturated carboxylic acid esters; Polymers of ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid; , Polyphosphazene, polyacrylonitrile and other polymer compounds with high ionic conductivity. The content of the organic binder is preferably 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass in total of the negative electrode material for the lithium ion secondary battery and the organic binder. The organic binder may be used alone or in combination of two or more. (Meta) acrylate means acrylate or methacrylate, and (meth) acrylonitrile means acrylonitrile or methacrylonitrile.
溶剤は、有機系結着剤を溶解又は分散可能な溶剤であれば特に制限されない。具体的には、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクトン等の有機溶剤が挙げられる。溶剤の使用量は、負極材スラリーをペースト等の所望の状態にできれば特に制限されない。例えば、負極材１００質量部に対して６０質量部以上１５０質量部未満であることが好ましい。 The solvent is not particularly limited as long as it is a solvent capable of dissolving or dispersing the organic binder. Specific examples thereof include organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and γ-butyrolactone. The amount of the solvent used is not particularly limited as long as the negative electrode material slurry can be brought into a desired state such as a paste. For example, it is preferably 60 parts by mass or more and less than 150 parts by mass with respect to 100 parts by mass of the negative electrode material.
負極材スラリーには、粘度を調整するための増粘剤を添加してもよい。増粘剤としては、カルボキシメチルセルロース、カルボキシメチルセルロースのナトリウム塩、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸、ポリアクリル酸のナトリウム塩、アルギン酸、アルギン酸のナトリウム塩、酸化スターチ、リン酸化スターチ、カゼイン等が挙げられる。増粘剤は１種単独で用いても、２種以上を組み合わせて用いてもよい。負極材スラリーが増粘剤を含む場合、その量は特に制限されない。増粘剤の含有量は、例えば、負極材１００質量部に対して０．１質量部〜５質量部であることが好ましい。 A thickener for adjusting the viscosity may be added to the negative electrode material slurry. As thickeners, carboxymethyl cellulose, sodium salt of carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid, sodium salt of polyacrylic acid, alginic acid, sodium salt of alginic acid, oxidized starch, phosphorus Examples include oxidized starch and casein. The thickener may be used alone or in combination of two or more. When the negative electrode material slurry contains a thickener, the amount thereof is not particularly limited. The content of the thickener is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the negative electrode material, for example.
負極材スラリーには、導電補助剤を添加してもよい。導電補助剤としては、天然黒鉛、人造黒鉛、カーボンブラック（アセチレンブラック、サーマルブラック、ファーネスブラック等）、導電性を示す酸化物、導電性を示す窒化物などが挙げられる。導電補助剤を含むことで、電極としての導電性をより向上させることができる。導電補助剤は１種単独で用いても、２種以上を組み合わせて用いてもよい。負極材スラリーが導電補助剤を含む場合、その量は特に制限されない。導電補助剤の含有量は、例えば、負極材１００質量部に対して０．５質量部〜１５質量部であることが好ましい。 A conductive auxiliary agent may be added to the negative electrode material slurry. Examples of the conductivity auxiliary agent include natural graphite, artificial graphite, carbon black (acetylene black, thermal black, furnace black, etc.), an oxide exhibiting conductivity, a nitride exhibiting conductivity, and the like. By including the conductive auxiliary agent, the conductivity as an electrode can be further improved. The conductive auxiliary agent may be used alone or in combination of two or more. When the negative electrode material slurry contains a conductive auxiliary agent, the amount thereof is not particularly limited. The content of the conductive auxiliary agent is preferably 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass of the negative electrode material, for example.
集電体の材質及び形状については、特に限定されず、例えば、アルミニウム、銅、ニッケル、チタン、ステンレス鋼等を、箔状、穴開け箔状、メッシュ状等にした帯状のものを用いればよい。また、ポーラスメタル（発泡メタル）、カーボンペーパー等の多孔性材料も使用可能である。 The material and shape of the current collector are not particularly limited, and for example, a strip of aluminum, copper, nickel, titanium, stainless steel, or the like in the form of a foil, a perforated foil, a mesh, or the like may be used. .. Further, porous materials such as porous metal (foam metal) and carbon paper can also be used.
負極材スラリーを集電体に塗布する方法は特に限定されず、公知の方法を適宜選択することができる。具体的には、メタルマスク印刷法、静電塗装法、ディップコート法、スプレーコート法、ロールコート法、ドクターブレード法、コンマコート法、グラビアコート法、スクリーン印刷法等が挙げられる。 The method of applying the negative electrode material slurry to the current collector is not particularly limited, and a known method can be appropriately selected. Specific examples thereof include a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a comma coating method, a gravure coating method, and a screen printing method.
負極の作製方法は特に制限されない。例えば、負極材と、結着剤と、必要に応じて添加される増粘剤、導電補助剤等と、溶剤とを含むペースト状の負極材スラリーを作製し、得られた負極材スラリーを集電体の上に塗布し、乾燥し、必要に応じてロールプレス等の成形法により圧縮成形することで作製することができる。その他、ペースト状の負極材スラリーをシート状、ペレット状等に成形し、これをロールプレス等の成形法により集電体と一体化することで作製することもできる。 The method for producing the negative electrode is not particularly limited. For example, a paste-like negative electrode material slurry containing a negative electrode material, a binder, a thickener added as needed, a conductive auxiliary agent, and a solvent is prepared, and the obtained negative electrode material slurry is collected. It can be produced by applying it on an electric body, drying it, and if necessary, compress-molding it by a molding method such as a roll press. In addition, it can also be produced by molding a paste-like negative electrode material slurry into a sheet shape, a pellet shape, or the like, and integrating this with a current collector by a molding method such as a roll press.
＜リチウムイオン二次電池＞
本実施形態のリチウムイオン二次電池は、本実施形態のリチウムイオン二次電池用負極と、正極と、電解質とを含む。本実施形態のリチウムイオン二次電池は、高容量である。
<Lithium-ion secondary battery>
The lithium ion secondary battery of the present embodiment includes a negative electrode for a lithium ion secondary battery of the present embodiment, a positive electrode, and an electrolyte. The lithium ion secondary battery of this embodiment has a high capacity.
リチウムイオン二次電池は、例えば、リチウムイオン二次電池用負極と正極とをセパレータを介して対向して配置し、電解液を注入することにより得ることができる。 The lithium ion secondary battery can be obtained, for example, by arranging the negative electrode and the positive electrode for the lithium ion secondary battery so as to face each other via a separator and injecting an electrolytic solution.
正極は、上述した負極と同様にして、集電体上に正極材料及び必要に応じて含まれる増粘剤、導電補助剤等を含む正極層を形成することで作製される。集電体としては、アルミニウム、チタン、ステンレス鋼等の金属又は合金を、箔状、穴開け箔状、メッシュ状等にしたものを用いることができる。 The positive electrode is produced by forming a positive electrode layer containing a positive electrode material and, if necessary, a thickener, a conductive auxiliary agent, etc., on the current collector in the same manner as the negative electrode described above. As the current collector, a metal or alloy such as aluminum, titanium, or stainless steel, which is in the form of a foil, a perforated foil, a mesh, or the like can be used.
正極層の形成に用いる正極材料は、特に制限されない。例えば、リチウムイオンをドーピング又はインターカレーション可能な金属化合物（金属酸化物、金属硫化物等）及び導電性高分子材料が挙げられる。より具体的には、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、マンガン酸リチウム（ＬｉＭｎＯ２）、これらの複酸化物（ＬｉＣｏｘＮｉｙＭｎｚＯ２、ｘ＋ｙ＋ｚ＝１）、添加元素Ｍ’を含む複酸化物（ＬｉＣｏａＮｉｂＭｎｃＭ’ｄＯ２、ａ＋ｂ＋ｃ＋ｄ＝１、Ｍ’：Ａｌ、Ｍｇ、Ｔｉ、Ｚｒ又はＧｅ）、スピネル型リチウムマンガン酸化物（ＬｉＭｎ２Ｏ４）、リチウムバナジウム化合物、Ｖ２Ｏ５、Ｖ６Ｏ１３、ＶＯ２、ＭｎＯ２、ＴｉＯ２、ＭｏＶ２Ｏ８、ＴｉＳ２、Ｖ２Ｓ５、ＶＳ２、ＭｏＳ２、ＭｏＳ３、Ｃｒ３Ｏ８、Ｃｒ２Ｏ５、オリビン型ＬｉＭＰＯ４（Ｍ：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅ）等のリチウム含有化合物、ポリアセチレン、ポリアニリン、ポリピロール、ポリチオフェン、ポリアセン等の導電性ポリマー、多孔質炭素などが挙げられる。正極材料は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 The positive electrode material used for forming the positive electrode layer is not particularly limited. Examples thereof include metal compounds (metal oxides, metal sulfides, etc.) capable of doping or intercalating lithium ions, and conductive polymer materials. More specifically, the lithium cobaltate (LiCoO 2), lithium nickelate (LiNiO 2), lithium manganate (LiMnO 2), these mixed oxide (LiCo x Ni y Mn z O 2, x + y + z = 1), 'mixed oxide containing (LiCo a Ni b Mn c M ' added element M d O 2, a + b + c + d = 1, M ': Al, Mg, Ti, Zr or Ge), spinel-type lithium manganese oxide (LiMn 2 O 4 ), Lithium vanadium compound, V 2 O 5 , V 6 O 13 , VO 2 , MnO 2 , TiO 2 , MoV 2 O 8 , TiS 2 , V 2 S 5 , VS 2 , MoS 2 , MoS 3 , Cr 3 Examples include lithium-containing compounds such as O 8 , Cr 2 O 5 , and olivine-type LiMPO 4 (M: Co, Ni, Mn, Fe), conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyacene, and porous carbon. Be done. As the positive electrode material, one type may be used alone, or two or more types may be used in combination.
正極は、正極材料と、結着剤と、結着剤を溶解又は分散可能な溶剤と、必要に応じて添加される増粘剤、導電補助剤等とを含む正極材スラリーを集電体の少なくとも一方の面に塗布し、次いで溶剤を乾燥して除去し、必要に応じて圧延して作製することができる。 The positive electrode is a collector of a positive electrode material slurry containing a positive electrode material, a binder, a solvent capable of dissolving or dispersing the binder, and a thickener, a conductive auxiliary agent, etc. added as needed. It can be made by applying to at least one surface, then drying and removing the solvent and rolling if necessary.
結着剤、溶剤、増粘剤及び導電補助剤としては、リチウムイオン二次電池用負極の項で例示したものを同様に用いることができる。 As the binder, the solvent, the thickener, and the conductive auxiliary agent, those exemplified in the section of the negative electrode for a lithium ion secondary battery can be similarly used.
リチウムイオン二次電池に用いられる電解質は特に制限されず、公知のものを用いることができる。例えば、電解質を有機溶剤に溶解させた電解液を用いることにより、非水系リチウムイオン二次電池を製造することができる。 The electrolyte used in the lithium ion secondary battery is not particularly limited, and known electrolytes can be used. For example, a non-aqueous lithium ion secondary battery can be manufactured by using an electrolytic solution in which an electrolyte is dissolved in an organic solvent.
電解質としては、ＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＢＦ４、ＬｉＣｌＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＡｌＯ４、ＬｉＡｌＣｌ４、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｌ、ＬｉＩ等が挙げられる。電解質は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 As the electrolyte, LiPF 6, LiClO 4, LiBF 4, LiClF 4, LiAsF 6, LiSbF 6, LiAlO 4, LiAlCl 4, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiC ( CF 3 SO 2 ) 3 , LiCl, LiI and the like can be mentioned. One type of electrolyte may be used alone, or two or more types may be used in combination.
有機溶剤としては、プロピレンカーボネート、エチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、ブチルメチルカーボネート、エチルプロピルカーボネート、ブチルエチルカーボネート、ジプロピルカーボネート、フルオロエチレンカーボネート、クロロエチレンカーボネート、ブチレンカーボネート、ビニレンカーボネート等のカーボネート系溶剤；γ−ブチロラクトン等のラクトン系溶剤；酢酸メチル、酢酸エチル、トリメチルリン酸エステル、トリエチルリン酸エステル等のエステル系溶剤：１，２−ジメトキシエタン、ジメチルエーテル、ジエチルエーテル等の鎖状エーテル系溶剤；テトラヒドロフラン、２−メチルテトラヒドロフラン、１，３−ジオキソラン、４−メチルジオキソラン等の環状エーテル系溶剤；スルホラン、３−メチルスルホラン、２，４−ジメチルスルホラン等のスルホラン系溶剤；ジメチルスルホキシド等のスルホキシド系溶剤；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド系溶剤；ジエチレングリコール等のポリオキシアルキレングリコール系溶剤；シクロペンタノン等のケトン系溶剤；シクロヘキシルベンゼン等の芳香族系溶剤；プロパンスルトン等の含硫黄系溶剤；３−メチル−１，３−オキサゾリジン−２−オン等のオキサゾリドン系溶剤などが挙げられる。有機溶剤は、１種を単独で用いても、２種以上を組み合わせて用いてもよい。 Examples of the organic solvent include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, fluoroethylene carbonate, chloroethylene carbonate, butylene. Carbonate solvents such as carbonate and vinylene carbonate; lactone solvents such as γ-butyrolactone; ester solvents such as methyl acetate, ethyl acetate, trimethyl phosphate, triethyl phosphate: 1,2-dimethoxyethane, dimethyl ether, diethyl Chain ether solvent such as ether; Cyclic ether solvent such as tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 4-methyldioxolane; Sulfolane solvent such as sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane Solvent; Sulfoxide solvent such as dimethyl sulfoxide; Nitrile solvent such as acetonitrile, propionitrile, benzonitrile; Amid solvent such as N, N-dimethylformamide, N, N-dimethylacetamide; Polyoxyalkylene glycol such as diethylene glycol Solvents; Ketone solvents such as cyclopentanone; Aromatic solvents such as cyclohexylbenzene; Sulfur-containing solvents such as propanesulton; Oxazolidene solvents such as 3-methyl-1,3-oxazolidin-2-one Can be mentioned. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
セパレータは特に制限されず、例えば、樹脂製の不織布、クロス、微孔フィルム又はそれらを組み合わせたものを使用することができる。樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィンを主成分とするものが挙げられる。リチウムイオン二次電池の構造上、正極と負極が直接接触しない場合は、セパレータは使用しなくてもよい。 The separator is not particularly limited, and for example, a non-woven fabric made of resin, a cloth, a micropore film, or a combination thereof can be used. Examples of the resin include those containing polyolefins such as polyethylene and polypropylene as main components. Due to the structure of the lithium ion secondary battery, if the positive electrode and the negative electrode do not come into direct contact, the separator may not be used.
本実施形態のリチウムイオン二次電池の作製方法は、本実施形態のリチウムイオン二次電池用負極を用いること以外は特に制限はなく、公知の正極、リチウムイオン二次電池用電解液、セパレータ等の材料を用いて、公知の方法により作製することができる。 The method for producing the lithium ion secondary battery of the present embodiment is not particularly limited except that the negative electrode for the lithium ion secondary battery of the present embodiment is used, and a known positive electrode, an electrolytic solution for a lithium ion secondary battery, a separator, etc. It can be produced by a known method using the materials of.
リチウムイオン二次電池における正極及び負極の状態は、特に限定されない。例えば、正極及び負極と、必要に応じて正極及び負極の間に配置されるセパレータとを、渦巻状に巻回した状態であっても、これらを平板状として積層した状態であってもよい。 The states of the positive electrode and the negative electrode in the lithium ion secondary battery are not particularly limited. For example, the positive electrode and the negative electrode and the separator arranged between the positive electrode and the negative electrode, if necessary, may be spirally wound or laminated as a flat plate.
リチウムイオン二次電池の形状は、特に制限されない。具体的には、ラミネート型電池、ペーパー型電池、ボタン型電池、コイン型電池、積層型電池、円筒型電池、角型電池等が挙げられる。 The shape of the lithium ion secondary battery is not particularly limited. Specific examples thereof include laminated batteries, paper batteries, button batteries, coin batteries, laminated batteries, cylindrical batteries, and square batteries.
本実施形態のリチウムイオン二次電池は、高容量であるため、電気自動車、パワーツール、電力貯蔵装置等に使用されるリチウムイオン二次電池として好適である。特に、加速性能及びブレーキ回生性能の向上のために大電流での充放電が求められている電気自動車（ＥＶ）、ハイブリッド電気自動車（ＨＥＶ）、プラグインハイブリッド電気自動車（ＰＨＥＶ）等に使用されるリチウムイオン二次電池として好適である。 Since the lithium ion secondary battery of the present embodiment has a high capacity, it is suitable as a lithium ion secondary battery used in electric vehicles, power tools, power storage devices, and the like. In particular, it is used in electric vehicles (EV), hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), etc., which are required to be charged and discharged with a large current in order to improve acceleration performance and brake regeneration performance. It is suitable as a lithium ion secondary battery.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
アスペクト比が１〜２０で、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子を用意した。このシリコン粒子を超音波処理によって解砕後、乾燥し、２５０メッシュの標準篩にて粗粉を除去して負極材試料１を得た。
(Example 1)
Flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less were prepared. The silicon particles were crushed by ultrasonic treatment, dried, and coarse powder was removed with a standard sieve of 250 mesh to obtain a negative electrode material sample 1.
（実施例２）
上記の実施例１で得られた負極材試料１を１００ｇとコールタールピッチ１０ｇを、それぞれ室温（２５℃）で混合し、次いで窒素流通下、３００℃／時間の昇温速度で９００℃まで昇温し、１時間保持して炭素層被覆シリコン粒子とした。得られた炭素被覆シリコン粒子を解砕後、２５０メッシュの標準篩を通し、負極材試料２を得た。
(Example 2)
100 g of the negative electrode material sample 1 obtained in Example 1 above and 10 g of coal tar pitch are mixed at room temperature (25 ° C.), and then raised to 900 ° C. at a heating rate of 300 ° C./hour under nitrogen flow. It was warmed and held for 1 hour to obtain carbon layer-coated silicon particles. The obtained carbon-coated silicon particles were crushed and passed through a standard sieve of 250 mesh to obtain a negative electrode material sample 2.
（実施例３）
上記の実施例２において、使用したコールタールピッチの量を２０ｇに代えた以外は、同様にして、負極材試料３を得た。
(Example 3)
A negative electrode material sample 3 was obtained in the same manner except that the amount of coal tar pitch used in Example 2 was replaced with 20 g.
（比較例１、２）
従来品である黒鉛系負極材試料（アスペクト比が１．１）を比較例１とし、従来品であるシリコン系負極材試料（アスペクト比が１．２又は１．７、厚みが０．５μｍ超）を比較例２とした。
(Comparative Examples 1 and 2)
A graphite-based negative electrode material sample (aspect ratio of 1.1), which is a conventional product, is used as Comparative Example 1, and a silicon-based negative electrode material sample (aspect ratio of 1.2 or 1.7, thickness of more than 0.5 μm), which is a conventional product, is used as Comparative Example 1. ) Was referred to as Comparative Example 2.
上記の実施例１〜３で得られた負極材試料１〜３、比較例１の黒鉛系負極材及び比較例２のシリコン系負極材の物性値、及び電気的特性を以下の方法で測定した。
測定結果を表１に示す。
The physical property values and electrical characteristics of the negative electrode material samples 1 to 3 obtained in Examples 1 to 3 above, the graphite-based negative electrode material of Comparative Example 1 and the silicon-based negative electrode material of Comparative Example 2 were measured by the following methods. ..
The measurement results are shown in Table 1.
［アスペクト比］
アスペクト比は、図１に示すように、シリコン粒子の長軸方向の長さをＡ、短軸方向の長さをＢとしたとき、Ａ／Ｂで表される。本明細書において、アスペクト比は、顕微鏡でシリコン粒子を拡大し、任意に１０個のシリコン粒子を選択してＡ／Ｂを測定して、その測定値の算術平均値をとったものである。
ここで、長軸方向の長さは、観察されるシリコン粒子を二本の平行線Ａ、Ａ’で接するように挟んだとき、その間隔が最も大きくなる場合のＡ、Ａ’間の距離であり、短軸方向の長さは、前記長軸方向の長さを決める二本の平行線Ａ、Ａ’に対して垂直な二本の平行線Ｂ、Ｂ’で前記シリコン粒子を接するよう挟んだときのそのＢ、Ｂ’間の距離である。
[aspect ratio]
As shown in FIG. 1, the aspect ratio is represented by A / B, where A is the length of the silicon particles in the major axis direction and B is the length in the minor axis direction. In the present specification, the aspect ratio is obtained by magnifying silicon particles with a microscope, arbitrarily selecting 10 silicon particles, measuring A / B, and taking an arithmetic mean value of the measured values.
Here, the length in the major axis direction is the distance between A and A'when the observed silicon particles are sandwiched so as to be in contact with two parallel lines A and A', and the interval is the largest. Yes, the length in the minor axis direction is sandwiched so that the silicon particles are in contact with the two parallel lines B, B'that are perpendicular to the two parallel lines A, A'that determine the length in the major axis direction. It is the distance between B and B'at that time.
［ラマンスペクトルピーク強度比（Ｒ値）］
レーザーラマン分光光度計（日本分光株式会社製、ＮＲＳ−２１００）を用い、レーザー出力１０ｍＷ、分光器Ｆシングル、入射スリット幅８００μｍ、積算回数３回及び露光時間６０秒の条件にて測定を行った。
[Raman spectrum peak intensity ratio (R value)]
Measurements were performed using a laser Raman spectrophotometer (NRS-2100, manufactured by Nippon Spectroscopy Co., Ltd.) under the conditions of a laser output of 10 mW, a spectroscope F single, an incident slit width of 800 μm, an integration number of 3 times, and an exposure time of 60 seconds. ..
［平均粒子径］
負極材試料２ｇを界面活性剤と共に精製水中に分散させた溶液を分取し、レーザー回折式粒度分布測定装置（株式会社島津製作所製、ＳＡＬＤ−３０００Ｊ）の試料水槽に入れた。次いで、超音波をかけながらポンプで循環させながら、レーザー回折式で測定した。得られた粒度分布の累積５０％粒子径（Ｄ５０）を平均粒子径とした。
[Average particle size]
A solution obtained by dispersing 2 g of a negative electrode material sample together with a surfactant in purified water was separated and placed in a sample water tank of a laser diffraction type particle size distribution measuring device (SALD-3000J, manufactured by Shimadzu Corporation). Then, it was measured by a laser diffraction method while circulating with a pump while applying ultrasonic waves. The cumulative 50% particle size (D 50 ) of the obtained particle size distribution was taken as the average particle size.
［比表面積］
負極材試料１ｇを２００℃で２時間真空乾燥した後、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡＳＡＰ２０１０を用い、液体窒素温度（７７Ｋ）での窒素吸着を多点法で測定、ＢＥＴ法に従って算出した。
[Specific surface area]
After vacuum drying 1 g of the negative electrode material sample at 200 ° C. for 2 hours, nitrogen adsorption at a liquid nitrogen temperature (77K) was measured by a multipoint method using ASAP2010 manufactured by Micromeritics, and calculated according to the BET method.
［初回充電容量及び初回効率］
負極材試料５質量％に対し、黒鉛系負極材料、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ９２．６質量％、１．２質量％及び１．２質量％となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００ μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ、対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電する１サイクル試験を行い、初回充電容量を測定した。さらに、得られた初回充電容量と初回放電容量の差から、初回効率を算出した。
[Initial charge capacity and initial efficiency]
Graphite-based negative electrode material, styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC) in solid content of 92.6% by mass, 1.2% by mass, and 1.2% by mass, respectively, with respect to 5% by mass of the negative electrode material sample. And kneaded to prepare a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil having a thickness of 10 μm using a quarter having a thickness of 100 μm, and further dried at 105 ° C. to remove water to prepare a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 was added to vinylene in a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC have a volume ratio of 3: 7). A coin battery was prepared by injecting a solution of an electrolytic solution dissolved so as to have a concentration of carbonate (VC) of 0.5 mol / L. Metallic lithium was used for the counter electrode, and a polyethylene micropore membrane having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, a constant current of 0.2 mA / cm 2 is charged to 0.02 V (V vs. Li / Li + ), and then a constant current of 0.2 V is applied. It was charged to 0.02 mA. Next, after a 30-minute rest period, a one-cycle test was conducted in which the battery was discharged to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2, and the initial charge capacity was measured. Furthermore, the initial efficiency was calculated from the difference between the obtained initial charge capacity and the initial discharge capacity.
［充電容量維持率（１０回）］
負極材試料５質量％に対し、黒鉛系負極材料、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ９２．６質量％、１．２質量％、及び、１．２質量％となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ、及び対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０ 分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電するサイクル試験を３回繰り返し行った。
その後、得られたコイン電池の試料電極と対極の間に、０．５ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．５Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．５ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電するサイクル試験を７回繰り返し行った。
１サイクル目の充電容量を１００％とし、１０回目の充電容量から、充電容量維持率（１０回）を算出した。
[Charging capacity maintenance rate (10 times)]
Graphite-based negative electrode material, styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC) were added in solid content to 92.6% by mass, 1.2% by mass, and 1.2, respectively, with respect to 5% by mass of the negative electrode material sample. It was added so as to be by mass% and kneaded to prepare a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil having a thickness of 10 μm using a quarter having a thickness of 100 μm, and further dried at 105 ° C. to remove water to prepare a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 was added to a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC have a volume ratio of 3: 7). A coin cell was prepared by injecting a solution of an electrolytic solution dissolved so as to have a concentration of vinylene carbonate (VC) of 0.5 mol / L. Metallic lithium was used for the counter electrode, and a polyethylene micropore membrane having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, a constant current of 0.2 mA / cm 2 is charged to 0.02 V (V vs. Li / Li + ), and then a constant current of 0.2 V is applied. It was charged to 0.02 mA. Next, after a rest time of 30 minutes, a cycle test of discharging to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2 was repeated three times.
Then, between the sample electrode and the counter electrode of the obtained coin battery, the battery is charged to 0.02 V (V vs. Li / Li + ) with a constant current of 0.5 mA / cm 2 , and then at a constant voltage of 0.5 V. It was charged until the current reached 0.02 mA. Next, after a rest period of 30 minutes, a cycle test of discharging to 1.5 V (V vs. Li / Li + ) at a constant current of 0.5 mA / cm 2 was repeated 7 times.
The charge capacity in the first cycle was set to 100%, and the charge capacity retention rate (10 times) was calculated from the charge capacity in the 10th cycle.
表１から明らかなように、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、比較例１及び比較例２のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池と比較して、初回充電容量に優れる。また、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、比較例２のシリコン系負極材料と比較し、初回効率及び充電容量維持率（１０回）に優れる。 As is clear from Table 1, the lithium ion secondary batteries using the negative electrode materials for lithium ion secondary batteries of Examples 1 to 3 use the negative negative materials for lithium ion secondary batteries of Comparative Examples 1 and 2. Compared to the existing lithium-ion secondary battery, it has excellent initial charge capacity. Further, the lithium ion secondary battery using the negative electrode material for the lithium ion secondary battery of Examples 1 to 3 has higher initial efficiency and charge capacity retention rate (10 times) than the silicon-based negative electrode material of Comparative Example 2. Excellent.
［初回充電容量と負極材試料中のシリコン粒子含有率との関係］
０〜５５質量％の負極材試料１に対し、スチレンブタジエンゴム（ＳＢＲ）、及び、カルボキシメチルセルロース（ＣＭＣ）を固形分でそれぞれ１．２質量％、残りが黒鉛系負極材料となるよう加え、混練してペースト状の負極材スラリーを作製した。このスラリーを厚さ１０μｍの電解銅箔に厚さ１００μｍのクオーターを用いて塗布し、さらに、１０５℃で乾燥して水分を除去し、試料電極（負極）を作製した。
次いで、上記試料電極、セパレータ及び対極（正極）の順に積層した後、ＬｉＰＦ６をエチレンカーボネート（ＥＣ）及びメチルエチルカーボネート（ＭＥＣ）（ＥＣとＭＥＣは体積比で３：７）の混合溶媒にビニレンカーボネート（ＶＣ）０．５ ｍｏｌ／Ｌの濃度になるように溶解した電解液溶液を注入し、コイン電池を作製した。対極には金属リチウムを使用し、セパレータには厚み２０μｍのポリエチレン微孔膜を使用した。
得られたコイン電池の試料電極と対極の間に、０．２ｍＡ／ｃｍ２の定電流で０．０２Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで充電し、次いで０．２Ｖの定電圧で電流が０．０２ｍＡになるまで充電した。次に３０分の休止時間後に０．２ｍＡ／ｃｍ２の定電流で１．５Ｖ（Ｖ ｖｓ. Ｌｉ／Ｌｉ＋）まで放電する１サイクル試験を行い、初回充電容量を測定した。
[Relationship between initial charge capacity and silicon particle content in negative electrode material sample]
Styrene butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were added to each of 0 to 55% by mass of the negative electrode material sample 1 in terms of solid content of 1.2% by mass, and the rest was added as a graphite-based negative electrode material and kneaded. To prepare a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil having a thickness of 10 μm using a quarter having a thickness of 100 μm, and further dried at 105 ° C. to remove water to prepare a sample electrode (negative electrode).
Next, after laminating the sample electrode, separator, and counter electrode (positive electrode) in this order, LiPF 6 was added to vinylene in a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC have a volume ratio of 3: 7). A coin cell was prepared by injecting a solution of an electrolytic solution dissolved so as to have a concentration of carbonate (VC) of 0.5 mol / L. Metallic lithium was used for the counter electrode, and a polyethylene micropore membrane having a thickness of 20 μm was used for the separator.
Between the sample electrode and the counter electrode of the obtained coin battery, a constant current of 0.2 mA / cm 2 is charged to 0.02 V (V vs. Li / Li + ), and then a constant current of 0.2 V is applied. It was charged to 0.02 mA. Next, after a 30-minute rest period, a one-cycle test was conducted in which the battery was discharged to 1.5 V (V vs. Li / Li + ) at a constant current of 0.2 mA / cm 2, and the initial charge capacity was measured.
負極材試料中のシリコン粒子含有率と初回充電容量との関係を表２及び図２に示す。 Table 2 and FIG. 2 show the relationship between the silicon particle content in the negative electrode material sample and the initial charge capacity.
表２及び図２から明らかなように、実施例１のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、シリコン粒子含有率の増加に伴い、初回充電容量が増加する。また、実施例２、３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池についても同様の結果が得られると推測される。 As is clear from Table 2 and FIG. 2, in the lithium ion secondary battery using the negative electrode material for the lithium ion secondary battery of Example 1, the initial charge capacity increases as the silicon particle content increases. Further, it is presumed that the same result can be obtained for the lithium ion secondary battery using the negative electrode material for the lithium ion secondary battery of Examples 2 and 3.
シリコン粒子のアスペクト比と初回充電容量との関係を表３及び図３に示す。なお、各実施例及び各比較例では、前述の［初回充電容量及び初回効率］と同様の方法により試料電極（負極）を形成し、かつ同様の方法で初回充電容量を測定した。 The relationship between the aspect ratio of the silicon particles and the initial charge capacity is shown in Table 3 and FIG. In each Example and each Comparative Example, the sample electrode (negative electrode) was formed by the same method as the above-mentioned [Initial charge capacity and initial efficiency], and the initial charge capacity was measured by the same method.
表３及び図３から明らかなように、実施例１〜３のリチウムイオン二次電池用負極材を用いたリチウムイオン二次電池は、負極材中のシリコン粒子のアスペクト比が２０以下であることにより、初回充電容量が増加する。 As is clear from Table 3 and FIG. 3, the lithium ion secondary battery using the negative electrode material for the lithium ion secondary battery of Examples 1 to 3 has an aspect ratio of silicon particles in the negative electrode material of 20 or less. As a result, the initial charge capacity increases.
以上より、アスペクト比が１〜２０で、かつ、厚みが０．５μｍ以下の扁平なシリコン粒子を適用した負極を有するリチウムイオン二次電池は、充電容量に優れる。さらに、比較例２のシリコン系負極材を用いたリチウムイオン二次電池よりも、高効率かつ長寿命である。 From the above, a lithium ion secondary battery having a negative electrode to which flat silicon particles having an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less is applied is excellent in charge capacity. Further, it has higher efficiency and longer life than the lithium ion secondary battery using the silicon-based negative electrode material of Comparative Example 2.
Claims (7)
体積平均粒子径（Ｄ ５０ ）が０．５μｍ〜１．３μｍであるリチウムイオン二次電池用負極材。 An aspect ratio of 1 to 20, and Ri Oh thickness in the 0.5μm or less and a minor axis direction length is 0.5μm or more flat silicon particles,
The volume average particle diameter (D 50) The negative electrode material for lithium-ion secondary battery Ru 0.5μm~1.3μm der.
前記シリコン粒子の表面上の少なくとも一部に形成された炭素層と、
を備え、
体積平均粒子径（Ｄ ５０ ）が０．５μｍ〜１．３μｍであるリチウムイオン二次電池用負極材。 Flat silicon particles with an aspect ratio of 1 to 20 and a thickness of 0.5 μm or less and a length in the minor axis direction of 0.5 μm or more.
A carbon layer formed on at least a part of the surface of the silicon particles and
Equipped with a,
The volume average particle diameter (D 50) The negative electrode material for lithium-ion secondary battery Ru 0.5μm~1.3μm der.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017000169A JP6938914B2 (en) | 2017-01-04 | 2017-01-04 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017000169A JP6938914B2 (en) | 2017-01-04 | 2017-01-04 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018110076A JP2018110076A (en) | 2018-07-12 |
| JP6938914B2 true JP6938914B2 (en) | 2021-09-22 |
Family
ID=62845203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017000169A Active JP6938914B2 (en) | 2017-01-04 | 2017-01-04 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6938914B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102461939B1 (en) * | 2018-04-05 | 2022-10-31 | 삼성에스디아이 주식회사 | Negative active material for recahrgeable lithium battery and recahrgeable lithium battery including the same |
| KR102211835B1 (en) | 2018-04-05 | 2021-02-02 | 삼성에스디아이 주식회사 | Negative active material for recahrgeable lithium battery and recahrgeable lithium battery including the same |
| US20220013764A1 (en) * | 2018-11-30 | 2022-01-13 | Panasonic Intellectual Property Management Co., Ltd. | Electrochemical device negative electrode and electrochemical device, and method for manufacturing electrochemical device negative electrode and method for manufacturing electrochemical device |
| KR20210103480A (en) | 2018-12-19 | 2021-08-23 | 디아이씨 가부시끼가이샤 | Silicon nanoparticles, active material for negative electrode of non-aqueous secondary battery using same, and secondary battery |
| KR102211237B1 (en) * | 2019-02-28 | 2021-02-02 | 삼성에스디아이 주식회사 | Negative active material composite for rechargeable lithium battery, method of preparing the same, negative electrode including the same and rechargeable lithium battery including the same |
| KR102461948B1 (en) * | 2019-02-28 | 2022-11-01 | 삼성에스디아이 주식회사 | Negative electrode for rechargeable lithium battery |
| EP3703163A1 (en) * | 2019-02-28 | 2020-09-02 | Samsung SDI Co., Ltd. | Negative active material composite for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same |
| KR102211236B1 (en) * | 2019-02-28 | 2021-02-02 | 삼성에스디아이 주식회사 | Negative active material composite for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same |
| CN111952550A (en) * | 2019-05-16 | 2020-11-17 | 贝特瑞新材料集团股份有限公司 | Core-shell type composite negative electrode material, and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5181002B2 (en) * | 2009-08-21 | 2013-04-10 | 尾池工業株式会社 | Scale-like thin film fine powder dispersion or scale-like thin film fine powder, paste using the same, battery electrode, and lithium secondary battery |
| EP2960971B1 (en) * | 2013-02-21 | 2020-04-22 | Connexx Systems Corporation | Composite active material for lithium secondary battery and method for producing same |
| GB2516895C (en) * | 2013-08-05 | 2019-05-15 | Nexeon Ltd | Structured particles |
| WO2015114692A1 (en) * | 2014-01-31 | 2015-08-06 | 株式会社豊田自動織機 | Negative electrode for nonaqueous secondary batteries; nonaqueous secondary battery; negative electrode active material; method for producing negative electrode active material; composite body comprising nano-silicon, carbon layer and cationic polymer layer; and method for producing composite body composed of nano-silicon and carbon layer |
| JP2015179593A (en) * | 2014-03-19 | 2015-10-08 | 株式会社豊田自動織機 | Negative electrode and power storage device |
| JP6503700B2 (en) * | 2014-11-21 | 2019-04-24 | 日立化成株式会社 | Negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery |
| JP6609909B2 (en) * | 2014-11-21 | 2019-11-27 | 日立化成株式会社 | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
-
2017
- 2017-01-04 JP JP2017000169A patent/JP6938914B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018110076A (en) | 2018-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6938914B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP6888722B2 (en) | Negative electrode material for lithium ion secondary battery, method for manufacturing negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP5927788B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP5439701B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery using the negative electrode material, and lithium ion secondary battery | |
| JP7279757B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP5811999B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery using the negative electrode material, and lithium ion secondary battery | |
| CN110870114A (en) | Method for producing negative electrode material for lithium ion secondary battery, and negative electrode material for lithium ion secondary battery | |
| JP7196938B2 (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP5590159B2 (en) | Negative electrode material for lithium ion secondary battery, production method thereof, negative electrode for lithium ion secondary battery using the negative electrode material, and lithium ion secondary battery | |
| JP2009187924A (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery using the negative electrode | |
| TWI752112B (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| JP7004093B2 (en) | Negative electrode material for lithium ion secondary battery, method for manufacturing negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery | |
| JP7226559B2 (en) | Method for producing negative electrode material for lithium ion secondary battery and method for producing lithium ion secondary battery | |
| JP7047892B2 (en) | Carbonaceous particles, negative material for lithium-ion secondary batteries, negative-negative materials for lithium-ion secondary batteries, and lithium-ion secondary batteries | |
| JP7416077B2 (en) | Negative electrode material for lithium ion secondary batteries and its manufacturing method, negative electrode for lithium ion secondary batteries, and lithium ion secondary batteries | |
| JP7226558B2 (en) | Method for producing negative electrode material for lithium ion secondary battery and method for producing lithium ion secondary battery | |
| JP2023047223A (en) | Lithium ion secondary battery negative electrode material, lithium ion secondary battery negative electrode, and lithium ion secondary battery | |
| CN116438691A (en) | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191114 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200708 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200728 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210302 |
|
| 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: 20210803 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210816 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6938914 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |