JP2019029317A - 二次電池 - Google Patents
二次電池 Download PDFInfo
- Publication number
- JP2019029317A JP2019029317A JP2017150950A JP2017150950A JP2019029317A JP 2019029317 A JP2019029317 A JP 2019029317A JP 2017150950 A JP2017150950 A JP 2017150950A JP 2017150950 A JP2017150950 A JP 2017150950A JP 2019029317 A JP2019029317 A JP 2019029317A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- secondary battery
- silicon
- battery
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 72
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 53
- 239000010703 silicon Substances 0.000 claims abstract description 53
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 239000007770 graphite material Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 40
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 230000007246 mechanism Effects 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- SLLLYZXUBOVDDR-UHFFFAOYSA-N but-2-yne-1-sulfonic acid Chemical compound CC#CCS(O)(=O)=O SLLLYZXUBOVDDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 description 65
- 150000002500 ions Chemical class 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 28
- 239000004065 semiconductor Substances 0.000 description 27
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- 239000011883 electrode binding agent Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 9
- 239000006104 solid solution Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- CGBHDYBKBMCNBL-UHFFFAOYSA-N prop-1-ynyl methanesulfonate Chemical compound CC#COS(C)(=O)=O CGBHDYBKBMCNBL-UHFFFAOYSA-N 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 230000005355 Hall effect Effects 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
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- 239000011521 glass Substances 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- 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 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000009782 nail-penetration test Methods 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- XSKXENAPYBDUCP-UHFFFAOYSA-N 2-oxobutane-1-sulfonic acid Chemical compound CCC(=O)CS(O)(=O)=O XSKXENAPYBDUCP-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- 229910014195 BM-400B Inorganic materials 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 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
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 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
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical group [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-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
- 238000006479 redox reaction Methods 0.000 description 1
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- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
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Abstract
【解決手段】二次電池は、第1電極(10)と、第2電極(20)と、セラミック材料を含有するセパレータと、電解質と、を備え、第2電極(20)は、粒径が30〜200nmのシリコン含有物質と、多層グラフェンと、グラファイト材料と、結着剤と、を含む。
【選択図】図1
Description
20≧ グラファイト材料重量/多層グラフェン重量 ≧3
30≧ シリコン含有物質重量/多層グラフェン重量 ≧4
ある実施形態において、電解質は、プロピニルメタンサルフォネートを含む。
Li1+x+yAlx(Ti,Ge)2-xSiyP3-yO12
20≧ グラファイト重量/グラフェン重量 ≧3
30≧ シリコン含有物質重量/グラフェン重量 ≧4
電極10は、アルカリ金属またはアルカリ土類金属を含有する複合酸化物を有している。例えば、アルカリ金属はリチウムおよびナトリウムの少なくとも1種であり、アルカリ土類金属はマグネシウムである。複合酸化物は、二次電池100の正極活物質として機能する。例えば、電極10は、複合酸化物および正極結着剤を混合した正極電極材から形成される。また、正極電極材には、さらに導電材が混合されてもよい。なお、複合酸化物は、1種類に限られず、複数種類であってもよい。
電極20は電極10において発生するイオンやホール、電子を吸蔵および放出可能である。電極20の活物質として、少なくともグラファイトとグラフェンとシリコン含有物を有し、加えて、各種天然黒鉛、人造黒鉛、シリコン系複合材料(シリサイド)、酸化シリコン系材料、チタン合金系材料、および各種合金組成材料を単独または混合して用いることができる。
20≧ グラファイト重量/グラフェン重量 ≧3
30≧ シリコン含有物質重量/グラフェン重量 ≧4
イオン伝達部材30は、液体、ゲル体および固体のいずれかである。イオン伝達部材30として、好適には、液体(電解液)が用いられる。その電解液には少なくともプロピニルメタンサルフォネート(propynyl methanesulfonate)を含むことが好ましい。
ホール伝達部材40は固体またはゲル体である。ホール伝達部材40は、電極10および電極20の少なくとも一方と接着されている。もしくは、電解質を介して接着されている。好ましくは、電解質は、ペロブスカイト構造を有する層を有する。これによって、充電時のシリコンの膨張により、ペロブスカイト層に圧力が加わり、ホール移動を加速させる機能が備わり、従来にない急速充電を可能とすることを見出した。
例えば、第1集電体110および第2集電体120はステンレス鋼もしくはニッケル箔から形成されている。これにより、低コストで電位幅を拡大させることができる。
住友スリーエム株式会社製ニッケルマンガンコバルト酸リチウムBC−618、株式会社クレハ製PVDF#1320(固形分12重量部のN−メチルピロリドン(NMP)溶液)、および、アセチレンブラックを重量比率3:1:0.09で、さらなるN−メチルピロリドン(NMP)とともに双腕式練合機にて攪拌し、正極電極材を作製した。厚さ13.3μmのアルミニウム箔に正極電極材を塗布して乾燥させた後、総厚が155μmとなるように圧延し、その後、特定の大きさに切り出して正極の電極を形成した。
ニッケル酸リチウム(住友金属鉱山株式会社製)にアンチモン(Sb)を0.7重量%ドープした材料、Li1.2MnPO4(Dow Chemical Company製のLithiated Metal Phosphate II)、および、Li2MnO3(Zhenhua E−Chem co.,ltd製のZHFL−01)をそれぞれ重量比率54.7重量%、18.2重量%、18.2重量%となるように混合し、ホソカワミクロン株式会社製のAMS−LAB(メカノフュージョン)において回転速度1500rpmで3分間処理し、電極10の活物質を作製した。次に、活物質、導電部材であるアセチレンブラック、および、アクリル基を有するポリアクリル酸モノマーからなる結着剤(日本ゼオン株式会社製SX9172)を固形分重量比率92:3:5で、N−メチルピロリドン(NMP)とともに双腕式練合機にて攪拌し、正極電極材を作製した。
ニッケル酸リチウム(JFEミネラル株式会社製)にアンチモン(Sb)(高純度科学製)を0.4重量%相当添加した材料に、導電部材であるグラフェン(XG Sciencess社製Graphene type-R)、および、アクリル基を有するポリアクリル酸モノマーからなる結着剤(日本ゼオン株式会社製SX9172)を固形分重量比率92:3:5で、N−メチルピロリドン(NMP)とともにプライミクス株式会社製薄膜旋回型高速ミキサーであるフィルミックスにて攪拌分散し、正極電極材を作製した。
実施例3では、実施例1においてシリコンを200nmより大きなものを用いて電池化した。今回、最小粒径210nm近傍で平均粒度227nmで500nm以下の粒径のシリコンを用いた。また、シリコンを30nmよりも小さなものは製造コストが2倍以上になり、生産上課題であるのが現状である。
比較例4では、実施例1においてグラファイト重量/グラフェン重量の比が3より小さい場合の電池であり、今回、この比が2.9の仕様の条件で電池を作製した。また、この3より小さい仕様は先行例の示すところも含まれることを意味する。
比較例5では、実施例1においてグラファイト重量/グラフェン重量の比が20よりも大きい場合の電池であり、今回、この比が21となる組成割合設計で電池化した。
比較例6では、シリコン/グラフェンの重量比が4よりも小さい場合である。今回、この比が3.9となるように組成割合設計して電池化した。また、先行例はこの範囲に含まれる。
比較例7では、シリコン/グラフェンの重量比が30よりも大きい場合である。今回は、この比が31となるように組成割合設計して電池化した。
実施例2では、実施例1の負極表面にN,N-ジメチルホルムアミド(DMF)に溶かしたPbI2溶液濃度40%をマイクログラビアで塗工乾燥し、更に、CH3NH3Iを2-プロパノールに濃度45%溶解させたものをその上からマイクログラビアで塗工乾燥し、更に、真空乾燥―100kPaの減圧下で105℃72時間保管したものを用いて電池化した。この手法で得た負極表面にはCH3NH3PbI3が4〜6μm程度形成できていることをTOF-SIMS等により確認した。
比較例1の仕様電位範囲2V−4.3Vにおける1C放電容量を100として各二次電池の容量比較性能評価を行った。また、電池の形状は、今回、角型電池缶を用い、積層電池とした。また、容量評価は2V−4.6Vの電位範囲でも各二次電池の容量比較性能評価を行った。さらに、10C/1Cの放電容量比を測定した。これによって、出力性能を評価する。同様に10C/1C充電容量比を測定した。これによって入力性能、急速充電性を評価する。
満充電した二次電池に対して、2.7mm径の鉄製丸釘を常温環境下で5mm/秒の速度で貫通させた時の発熱状態及び外観を観測した。下記表1に結果を示す。表1では、二次電池の温度及び外観の変化が生じなかった二次電池を「OK」と示し、二次電池の温度及び外観の変化が生じた二次電池を「NG」と示している。
充電率200%を電流維持し、15分以上外観に変化が生じるか否かを判定した。下記表1に結果を示す。表1では、異常を起こさなかった二次電池を「OK」と示し、変化(膨れまたは破裂等)が生じた二次電池を「NG」と示している。
実施例1、実施例2及び比較例1から比較例7の二次電池を仕様電位範囲2V−4.3V仕様の場合、25℃で1C/4.3Vで充電した後、1C/2V放電を3000サイクル及び1万サイクル実施し、初回目の容量に対して容量低下を比較した。
表1に上述した評価結果を示す。
20 第2電極
30 イオン伝達部材
40 ホール伝達部材
100 二次電池
20≧ グラファイト材料重量/多層グラフェン重量 ≧3
30≧ シリコン含有物質重量/多層グラフェン重量 ≧4
20≧ グラファイト材料重量/多層グラフェン重量 ≧3
30≧ シリコン含有物質重量/多層グラフェン重量 ≧4
比較例3では、実施例1においてシリコンを200nmより大きなものを用いて電池化した。今回、最小粒径210nm近傍で平均粒度227nmで500nm以下の粒径のシリコンを用いた。また、シリコンを30nmよりも小さなものは製造コストが2倍以上になり、生産上課題であるのが現状である。
Claims (8)
- 第1電極と、第2電極と、セラミック材料を含有するセパレータと、電解質と、を備え、前記第2電極は、粒径が30〜200nmのシリコン含有物質と、多層グラフェンと、グラファイト材料と、結着剤と、を含む二次電池。
- 前記第2電極は、前記グラファイト材料と前記多層グラフェンの重量比及び前記シリコン含有物質と前記多層グラフェンの重量比が以下の割合である請求項1に記載の二次電池。
20≧ グラファイト材料重量/多層グラフェン重量 ≧3
30≧ シリコン含有物質重量/多層グラフェン重量 ≧4 - 前記電解質は、プロピニルメタンサルフォネートを含む請求項1又は2に記載の二次電池。
- 前記電解質は、固体電解質であり、燐と硫黄元素を含有する請求項1又は2に記載の二次電池。
- 前記電解質は、ペロブスカイト構造を有する層を有する請求項1、2、及び4のいずれか一つに記載の二次電池。
- 前記ペロブスカイト構造を有する層は、鉛元素とヨウ素元素を含有している請求項5に記載の二次電池。
- 前記シリコン含有物質が充電時に膨張することでペロブスカイト層に外力が加わることで蓄電機構が発現する機構を有する請求項5又は6に記載の二次電池。
- 前記第1電極は、リチウムとニッケルを含有する材料により成る請求項1から7のいずれか一つに記載の二次電池。
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JP2021157881A (ja) * | 2020-03-25 | 2021-10-07 | 株式会社パワーフォー | 二次電池 |
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WO2020137912A1 (ja) * | 2018-12-28 | 2020-07-02 | 株式会社パワーフォー | 二次電池 |
JP2020109735A (ja) * | 2018-12-28 | 2020-07-16 | 株式会社パワーフォー | 二次電池 |
EP3760386A1 (en) | 2019-06-17 | 2021-01-06 | Makita Corporation | Battery-powered portable tool |
US11233282B2 (en) | 2019-06-17 | 2022-01-25 | Makita Corporation | Battery-powered portable tool |
US11955615B2 (en) | 2019-06-17 | 2024-04-09 | Makita Corporation | Battery-powered portable tool |
Also Published As
Publication number | Publication date |
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EP3553850A4 (en) | 2020-07-01 |
US20200006753A1 (en) | 2020-01-02 |
EP3553850A1 (en) | 2019-10-16 |
JP6518734B2 (ja) | 2019-05-22 |
WO2019027016A1 (ja) | 2019-02-07 |
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