WO2022050252A1 - 全固体二次電池用合剤、全固体二次電池用合剤シート及びその製造方法並びに全固体二次電池 - Google Patents
全固体二次電池用合剤、全固体二次電池用合剤シート及びその製造方法並びに全固体二次電池 Download PDFInfo
- Publication number
- WO2022050252A1 WO2022050252A1 PCT/JP2021/031852 JP2021031852W WO2022050252A1 WO 2022050252 A1 WO2022050252 A1 WO 2022050252A1 JP 2021031852 W JP2021031852 W JP 2021031852W WO 2022050252 A1 WO2022050252 A1 WO 2022050252A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid
- state secondary
- secondary battery
- sheet
- mixture
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 142
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 41
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 99
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 99
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 65
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 57
- 239000011230 binding agent Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 238000005096 rolling process Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 239000011163 secondary particle Substances 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 230000005484 gravity Effects 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 description 45
- 239000002184 metal Substances 0.000 description 45
- 239000007774 positive electrode material Substances 0.000 description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 29
- 229910052744 lithium Inorganic materials 0.000 description 23
- 229910052799 carbon Inorganic materials 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 239000011164 primary particle Substances 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 239000011149 active material Substances 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 13
- 229910052723 transition metal Inorganic materials 0.000 description 13
- 239000011888 foil Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 150000001340 alkali metals Chemical class 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 229910052733 gallium Inorganic materials 0.000 description 8
- 229910052732 germanium Inorganic materials 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229910001386 lithium phosphate Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 206010061592 cardiac fibrillation Diseases 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 230000002600 fibrillogenic effect Effects 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229910052789 astatine Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000002931 mesocarbon microbead Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019271 La0.55Li0.35TiO3 Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910008731 Li2O-Al2O3-SiO2-P2O5-TiO2 Inorganic materials 0.000 description 1
- 229910008547 Li2O—Al2O3—SiO2—P2O5—TiO2 Inorganic materials 0.000 description 1
- 229910008550 Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2 Inorganic materials 0.000 description 1
- 229910009324 Li2S-SiS2-Li3PO4 Inorganic materials 0.000 description 1
- 229910009326 Li2S-SiS2-Li4SiO4 Inorganic materials 0.000 description 1
- 229910009328 Li2S-SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007295 Li2S—SiS2—Li3PO4 Inorganic materials 0.000 description 1
- 229910007290 Li2S—SiS2—Li4SiO4 Inorganic materials 0.000 description 1
- 229910013950 Li3.25P0.25Ge0.76S4 Inorganic materials 0.000 description 1
- 229910012266 Li3.4P0.6Si0.4S4 Inorganic materials 0.000 description 1
- 229910012323 Li3.5Zn0.25GeO4 Inorganic materials 0.000 description 1
- 229910012329 Li3BO3—Li2SO4 Inorganic materials 0.000 description 1
- 229910012847 Li3PS4-Li4GeS4 Inorganic materials 0.000 description 1
- 229910012840 Li3PS4—Li4GeS4 Inorganic materials 0.000 description 1
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010701 LiFeP Inorganic materials 0.000 description 1
- 229910010835 LiI-Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910010840 LiI—Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910010855 LiI—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910010853 LiI—Li2S—SiS2—P2S5 Inorganic materials 0.000 description 1
- 229910010847 LiI—Li3PO4-P2S5 Inorganic materials 0.000 description 1
- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910020346 SiS 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GIPIUENNGCQCIT-UHFFFAOYSA-K cobalt(3+) phosphate Chemical class [Co+3].[O-]P([O-])([O-])=O GIPIUENNGCQCIT-UHFFFAOYSA-K 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present disclosure relates to an all-solid-state secondary battery mixture, an all-solid-state secondary battery mixture sheet and a method for producing the same, and an all-solid-state secondary battery.
- an all-solid-state secondary battery sheet is produced by applying and drying a slurry obtained by mixing a binder and a solvent with an electrode active material and a conductive auxiliary agent. Is commonly done.
- the polytetrafluoroethylene resin is a polymer that is easily fibrillated, and it is also used as a binder by fibrillating it.
- Patent Document 1 discloses a method for producing an electrode for fibrillating polytetrafluoroethylene by subjecting a mixture containing an active material and a polytetrafluoroethylene mixed binder material to a high shear treatment with a jet mill.
- an all-solid-state secondary battery mixture having good properties an all-solid-state secondary battery mixture sheet containing the mixture, and the all-solid-state secondary battery sheet are used. It is an object of the present invention to provide an all-solid-state secondary battery. Another object of the present disclosure is to provide a method for producing a sheet for an all-solid-state secondary battery containing a polytetrafluoroethylene resin having a fine fiber structure.
- the present disclosure is an all-solid-state secondary battery mixture containing a solid electrolyte and a binder.
- the binder is a polytetrafluoroethylene resin
- Polytetraluoloethylene resin is an all-solid-state secondary battery mixture characterized by having a fibrous structure having a fibril diameter (median) of 70 nm or less.
- the all-solid-state secondary battery mixture is preferably for a lithium-ion all-solid-state secondary battery.
- the all-solid-state secondary battery mixture is preferably for a sulfide-based all-solid-state secondary battery.
- the all-solid-state secondary battery mixture is an all-solid-state secondary battery mixture obtained by using a raw material composition containing a solid electrolyte and a binder, and the raw material composition is a binder. Is preferably a powdered polytetrafluoroethylene resin.
- the raw material composition preferably contains substantially no liquid medium.
- the powdery polytetrafluoroethylene resin preferably has a water content of 500 ppm or less.
- the powdery polytetrafluoroethylene resin preferably has a standard specific gravity of 2.11 to 2.20.
- the powdered polytetrafluoroethylene resin preferably contains 50% by mass or more of the polytetrafluoroethylene resin having a secondary particle diameter of 500 ⁇ m or more.
- the powdered polytetrafluoroethylene resin preferably contains 80% by mass or more of the polytetrafluoroethylene resin having a secondary particle diameter of 500 ⁇ m or more.
- the present disclosure is also an all-solid-state secondary battery mixture sheet containing the above-mentioned all-solid-state secondary battery mixture.
- the present disclosure is a step of applying a shearing force while mixing a raw material composition containing a solid electrolyte and a binder (1).
- Step of rolling into a shape (3) A method for producing a mixture sheet for an all-solid-state secondary battery, wherein the binder is a powdered polytetrafluoroethylene resin. But it is also.
- the present disclosure is also an all-solid-state secondary battery having the above-mentioned mixture sheet for an all-solid-state secondary battery.
- PTFE polytetrafluoroethylene resin
- Batteries can be manufactured. Further, in the production method of the present disclosure, a mixture sheet for an all-solid-state secondary battery containing a polytetrafluoroethylene resin having a fine fiber structure can be produced, and a slurry is not produced. The load on the process can be reduced.
- the present disclosure provides an all-solid-state secondary battery mixture and a mixture sheet containing the same, which can be suitably used in an all-solid-state secondary battery.
- PTFE is used as a binder.
- a solvent-soluble resin such as a copolymer of vinylidene fluoride and hexafluoropropylene is used as a binder, and a slurry containing the resin is applied and dried.
- a method for preparing a mixture for an all-solid-state secondary battery was used.
- PTFE can be used as a binder. That is, the fibrillated PTFE is entangled with other powder components and the like to bind the powder components, whereby it can act as a binder when molding the powder components.
- the fibrillated PTFE is used as a binder, good performance cannot be exhibited when it is used as a mixture for an all-solid-state secondary battery unless the fibrillation is sufficient.
- this point is examined, and the fibrillated PTFE is completely formed by performing a fine fibrillation process so that the PTFE has a fibrous structure having a fibril diameter (median value) of 70 nm or less.
- a binder for a solid-state secondary battery mixture As a binder for a solid-state secondary battery mixture, deterioration of the solid electrolyte can be reduced and good performance can be exhibited.
- the all-solid-state secondary battery mixture of the present disclosure is obtained by using a raw material composition containing an electrode active material and a binder, and the binder is preferably powdery PTFE. Since the PTFE powder is used as the raw material instead of the PTFE aqueous dispersion, the water content derived from the raw material is small in the all-solid-state secondary battery mixture, and there is no problem due to the mixing of the water content. It also has the advantage of improving battery performance. In addition, it can be a battery having excellent ion conduction.
- the raw material composition does not substantially contain a liquid medium.
- the all-solid-state secondary battery mixture of the present disclosure has an advantage that no solvent is used in the production. That is, in the conventional method for forming a mixture for an all-solid-state secondary battery, a slurry in which powder, which is a component of the mixture for an all-solid-state secondary battery, is dispersed is prepared by using a solvent in which a binder is dissolved. It was common to prepare a mixture sheet for an all-solid-state secondary battery by applying and drying the slurry. In this case, a solvent that dissolves the binder is used.
- the solvent that can dissolve the binder resin that has been generally used in the past is limited to a specific solvent such as butyl butyrate, and these deteriorate the solid electrolyte and cause a decrease in battery performance.
- the binder resin that dissolves in a low-polarity solvent such as heptane is very limited, and the flash point is low, which makes handling complicated.
- the all-solid-state secondary battery mixture of the present disclosure has a PTFE having a fibrous structure having a fibril diameter (median) of 70 nm or less as a component.
- fibril diameter (median) it is important that the fibril diameter (median) is 70 nm or less.
- PTFE having a small fibril diameter is present in the all-solid-state secondary battery mixture, and this acts to bind the powders of the components constituting the all-solid-state secondary battery mixture to each other. It achieves the object of the invention.
- the fibril diameter (median) is a value measured by the following method. (1) Using a scanning electron microscope (S-4800 type manufactured by Hitachi, Ltd.), an enlarged photograph (7000 times) of the mixture sheet for an all-solid-state secondary battery is taken to obtain an image. (2) Draw two lines horizontally at equal intervals on this image and divide the image into three equal parts. (3) For all the PTFE fibers on the upper straight line, the diameters of three points per PTFE fiber are measured, and the average value is taken as the diameter of the PTFE fiber. For the three points to be measured, select the intersection of the PTFE fiber and the straight line, and the location shifted up and down by 0.5 ⁇ m from the intersection. (Excluding unfibered PTFE primary particles).
- the fibril diameter is preferably 65 nm or less, and more preferably 62 nm or less. It should be noted that if fibrilization is promoted too much, flexibility tends to be lost.
- the lower limit is not particularly limited, but from the viewpoint of strength, it is preferably, for example, 15 nm or more, and more preferably 20 nm or more.
- the method for obtaining PTFE having the above-mentioned fibril diameter (median value) is not particularly limited, but for example, Step of applying shearing force while mixing a raw material composition containing a solid electrolyte and a binder (1)
- Examples thereof include a method performed by the step (3) of rolling into a shape.
- the step (1) by setting the mixing condition of the raw material composition to 1000 rpm or less, it is possible to proceed with the fibrillation of PTFE while maintaining the flexibility, and the shear stress to be given can be increased.
- the fibril diameter (median value) of PTFE can be 70 nm or less.
- the fibril diameter is also adjusted by having a step (5) in which the obtained rolled sheet is roughly crushed, then molded into a bulk shape again, and rolled into a sheet shape. can do.
- the step (5) is preferably repeated, for example, once or more and 12 times or less.
- the PTFE powder is made into fibril, which is entangled with a powder component such as a solid electrolyte, so that a mixture for an all-solid secondary battery can be produced.
- a powder component such as a solid electrolyte
- the PTFE resin is not particularly limited, and may be a homopolymer or a copolymer that can be fibrillated.
- examples of the fluorine atom-containing monomer as a comonomer include chlorotrifluoroethylene, hexafluoropropylene, fluoroalkylethylene, perfluoroalkylethylene, fluoroalkyl / fluorovinyl ether and the like.
- PTFE powder does not mean a dispersed state mixed with a liquid medium, but a solid state as a powder.
- the object of the present disclosure can be suitably achieved by producing a mixture for an all-solid-state secondary battery using PTFE in such a state and using PTFE in the absence of a liquid medium.
- the powder-shaped PTFE used as a raw material for preparing the all-solid-state secondary battery mixture of the present disclosure preferably has a water content of 500 ppm or less.
- a water content of 500 ppm or less is preferable in that deterioration of the solid electrolyte is reduced.
- the water content is more preferably 300 ppm or less.
- the powder-shaped PTFE used as a raw material for preparing the all-solid-state secondary battery mixture of the present disclosure preferably has a standard specific gravity of 2.11 to 2.20.
- the standard specific gravity is within the range, there is an advantage in that a high-strength electrode mixture sheet can be produced.
- the lower limit of the standard specific gravity is more preferably 2.12 or more.
- the upper limit of the standard specific gravity is more preferably 2.19 or less, and further preferably 2.18 or less.
- the standard specific density [SSG] is prepared in accordance with ASTM D-4895-89, and the specific gravity of the obtained sample is measured by the water substitution method.
- the powdery PTFE preferably contains 50% by mass or more of a polytetrafluoroethylene resin having a secondary particle diameter of 500 ⁇ m or more, and more preferably 80% by mass or more.
- a polytetrafluoroethylene resin having a secondary particle diameter of 500 ⁇ m or more is within the range, there is an advantage that a high-strength mixture sheet can be produced.
- PTFE having a secondary particle diameter of 500 ⁇ m or more By using PTFE having a secondary particle diameter of 500 ⁇ m or more, a mixture sheet having lower resistance and rich toughness can be obtained.
- the lower limit of the secondary particle size of the powdered PTFE is more preferably 300 ⁇ m, further preferably 350 ⁇ m.
- the upper limit of the secondary particle diameter is more preferably 700 ⁇ m or less, and further preferably 600 ⁇ m or less.
- the secondary particle size can be obtained by, for example, a sieving method.
- the powdery PTFE preferably has an average primary particle diameter of 150 nm or more because an electrode mixture sheet having higher strength and excellent homogeneity can be obtained. It is more preferably 180 nm or more, further preferably 210 nm or more, and particularly preferably 220 nm or more.
- the upper limit is not particularly limited, but may be 500 nm. From the viewpoint of productivity in the polymerization step, 350 nm is preferable.
- the average primary particle size is the transmission rate of projected light at 550 nm with respect to the unit length of the aqueous dispersion whose polymer concentration is adjusted to 0.22% by mass using the aqueous dispersion of PTFE obtained by polymerization, and the transmission type.
- a calibration curve with the average primary particle diameter determined by measuring the directional diameter in the electron micrograph was prepared, the permeability of the aqueous dispersion to be measured was measured, and the calibration curve was determined based on the calibration curve. can.
- the PTFE used in the present disclosure may have a core-shell structure.
- the PTFE having a core-shell structure include polytetrafluoroethylene containing a core of high molecular weight polytetrafluoroethylene in the particles and a shell of lower molecular weight polytetrafluoroethylene or modified polytetrafluoroethylene. ..
- modified polytetrafluoroethylene include polytetrafluoroethylene described in JP-A-2005-527652.
- a powder-shaped PTFE that satisfies each of the above-mentioned parameters can be obtained by a conventional production method.
- it may be manufactured according to the manufacturing method described in International Publication No. 2015-080291, International Publication No. 2012-086710, and the like.
- the lower limit of the content of the binder is preferably 0.2% by mass or more, more preferably 0.3% by mass or more in the all-solid-state secondary battery mixture. It is more preferably more than 1.0% by mass.
- the upper limit of the content of the binder is preferably 10% by mass or less, more preferably 6.0% by mass or less in the all-solid-state secondary battery mixture.
- the solid electrolyte used in the all-solid-state secondary battery mixture of the present disclosure may be a sulfide-based solid electrolyte or an oxide-based solid electrolyte.
- a sulfide-based solid electrolyte when used, it has an advantage of being flexible.
- the sulfide-based solid electrolyte preferably contains lithium.
- Lithium-containing sulfide-based solid electrolytes are used in solid-state batteries that use lithium ions as carriers, and are particularly preferable in terms of electrochemical devices having a high energy density.
- the oxide-based solid electrolyte is preferably a compound containing an oxygen atom (O), having ionic conductivity of a metal belonging to Group 1 or Group 2 of the Periodic Table, and having electron insulating properties. ..
- O oxygen atom
- Onb (M bb is at least one element of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, Sn, xb satisfies 5 ⁇ xb ⁇ 10, and yb is 1 ⁇ .
- yb ⁇ 4 is satisfied, zb is 1 ⁇ zb ⁇ 4, mb is 0 ⁇ mb ⁇ 2, nb is 5 ⁇ nb ⁇ 20), Li xc Byc M cc zc Onc (M cc ). Is at least one element of C, S, Al, Si, Ga, Ge, In, Sn, xc satisfies 0 ⁇ xc ⁇ 5, yc satisfies 0 ⁇ yc ⁇ 1, and zc satisfies 0 ⁇ zc.
- nc satisfies 0 ⁇ nc ⁇ 6
- Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P mdOnd however, 1 ⁇ xd ⁇ 3, 0 ⁇ yd ⁇ 2 , 0 ⁇ zd ⁇ 2, 0 ⁇ ad ⁇ 2 , 1 ⁇ md ⁇ 7, 3 ⁇ nd ⁇ 15)
- Dee represents a halogen atom or a combination of two or more kinds of halogen atoms), Li xf Si yf Ozf (1 ⁇ xf ⁇ 5, 0 ⁇ yf ⁇ ). 3, 1 ⁇ zf ⁇ 10), Li xg S syg O zg (1 ⁇ xg ⁇ 3, 0 ⁇ yg ⁇ 2, 1 ⁇ zg ⁇ 10), Li 3 BO 3 ⁇ Li 2 SO 4 , Li 2 OB 2 O 3 -P 2 O 5 , Li 2 O-SiO 2 , Li 6 BaLa 2 Ta 2 O 12 , Li 3 PO (4-3 / 2w) N w (w is w ⁇ 1), Lithium super ionic Li 3.5 Zn 0.25 GeO 4 with compound) type crystal structure, La 0.51 Li 0.34 TIM 2.94 with perovskite type crystal structure, La 0.55 Li 0.35 TiO 3 , NASICON ( LiTi 2 P 3 O 12 , Li 1 + xh +
- a ceramic material in which element substitution is performed on LLZ is also known.
- LLZ-based ceramic materials subjected to element substitution can also be mentioned.
- a phosphorus compound containing Li, P and O is also desirable.
- lithium phosphate Li 3 PO 4
- LiPON in which a part of oxygen of lithium phosphate is replaced with nitrogen
- LiPOD 1 LiPOD 1
- D 1 is Ti, V, Cr, Mn, Fe, Co, Ni, Cu
- LiA 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like
- a 1 ON A 1 is at least one selected from Si, B, Ge, Al, C, Ga and the like
- Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 -GeO 2 Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 .
- Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 can be mentioned.
- the oxide-based solid electrolyte preferably contains lithium.
- Lithium-containing oxide-based solid electrolytes are used in solid-state batteries that use lithium ions as carriers, and are particularly preferable in terms of electrochemical devices having a high energy density.
- the oxide-based solid electrolyte is preferably an oxide having a crystal structure.
- Oxides having a crystalline structure are particularly preferred in terms of good Li ion conductivity.
- Oxides having a crystal structure include perovskite type (La 0.51 Li 0.34 TIM 2.94 , etc.), NASICON type (Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , etc.), and Examples include a garnet type (Li 7 La 3 Zr 2 O 12 (LLZ), etc.). Of these, the NASICON type is preferable.
- the volume average particle size of the oxide-based solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.03 ⁇ m or more.
- the upper limit is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the average particle size of the oxide-based solid electrolyte particles is measured by the following procedure. Oxide-based solid electrolyte particles are diluted with 1% by mass of a dispersion in a 20 ml sample bottle with water (heptane in the case of a water-unstable substance). The diluted dispersed sample is irradiated with 1 kHz ultrasonic waves for 10 minutes, and immediately after that, it is used for the test.
- the all-solid-state secondary battery mixture of the present disclosure is particularly suitable for lithium-ion all-solid-state secondary batteries. It is also suitable for sulfide-based all-solid-state secondary batteries.
- the all-solid-state secondary battery mixture of the present disclosure is usually used in the form of a sheet when used in an all-solid-state secondary battery.
- the all-solid-state secondary battery mixture sheet of the present disclosure may be a positive electrode sheet or a negative electrode sheet. Further, it can be used as a sheet for a solid electrolyte layer. Of these, when the sheet is used as an electrode sheet, it further contains active material particles.
- the active material particles can be a positive electrode active material or a negative electrode active material.
- the all-solid-state secondary battery sheet of the present disclosure can be more preferably used as a positive electrode sheet using a positive electrode active material. Further, when the electrode sheet is used, it may contain a conductive auxiliary agent, if necessary.
- the electrode active material the conductive auxiliary agent, and the like will be described.
- a positive electrode active material is blended in the all-solid-state secondary battery mixture sheet.
- a positive electrode active material known as a positive electrode active material of a solid-state battery can be applied.
- a positive electrode active material that can occlude and release lithium ions.
- the positive electrode active material is not particularly limited as long as it can electrochemically occlude and release alkali metal ions, but for example, a material containing an alkali metal and at least one transition metal is preferable.
- an alkali metal-containing transition metal composite oxide examples include an alkali metal-containing transition metal composite oxide, an alkali metal-containing transition metal phosphoric acid compound, and a conductive polymer.
- an alkali metal-containing transition metal composite oxide that produces a high voltage is particularly preferable.
- the alkali metal ion examples include lithium ion, sodium ion, potassium ion and the like.
- the alkali metal ion can be a lithium ion. That is, in this embodiment, the alkali metal ion secondary battery is a lithium ion secondary battery.
- alkali metal-containing transition metal composite oxide examples include, for example.
- Formula: Ma Mn 2-b M 1 b O 4 (In the formula, M is at least one metal selected from the group consisting of Li, Na and K; 0.9 ⁇ a; 0 ⁇ b ⁇ 1.5; M 1 is Fe, Co, Ni, Alkali metal / manganese represented by (at least one metal selected from the group consisting of Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge).
- MNi 1-c M 2 cO 2 (In the formula, M is at least one metal selected from the group consisting of Li, Na and K; 0 ⁇ c ⁇ 0.5; M 2 is Fe, Co, Mn, Cu, Zn, Al, An alkali metal / nickel composite oxide represented by (at least one metal selected from the group consisting of Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge), or Formula: MCo 1-d M 3 d O 2 (In the formula, M is at least one metal selected from the group consisting of Li, Na and K; 0 ⁇ d ⁇ 0.5; M 3 is Fe, Ni, Mn, Cu, Zn, Al, At least one metal selected from the group consisting of Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge) Examples thereof include an alkali metal / cobalt composite oxide represented by. In the above, M is preferably one kind of
- MCoO 2 , MMnO 2 , MNiO 2 , MMn 2 O 4 , MNi 0.8 Co 0.15 Al 0.05 O 2 or MNi 1/3 Co 1/3 Mn 1/3 O 2 and the like are preferable, and the compound represented by the following general formula (3) is preferable.
- Examples of the alkali metal-containing transition metal phosphoric acid compound include the following formula (4).
- M e M 4 f (PO 4 ) g (4) (
- M is at least one metal selected from the group consisting of Li, Na and K
- M4 is selected from the group consisting of V, Ti, Cr, Mn, Fe, Co, Ni and Cu.
- the compound represented by 0.5 ⁇ e ⁇ 3, 1 ⁇ f ⁇ 2, 1 ⁇ g ⁇ 3) is mentioned.
- M is preferably one kind of metal selected from the group consisting of Li, Na and K, more preferably Li or Na, and even more preferably Li.
- the transition metal of the lithium-containing transition metal phosphoric acid compound is preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu or the like, and specific examples thereof include, for example, LiFePO 4 , Li 3 Fe 2 (PO 4 ). 3. Iron phosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and some of the transition metal atoms that are the main constituents of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn. , Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other elements.
- the lithium-containing transition metal phosphoric acid compound preferably has an olivine-type structure.
- positive electrode active materials include MFePO 4 , MNi 0.8 Co 0.2 O 2 , M 1.2 Fe 0.4 Mn 0.4 O 2 , MNi 0.5 Mn 1.5 O 2 , and MV 3 .
- examples thereof include O 6 and M 2 MnO 3 (in the formula, M is at least one metal selected from the group consisting of Li, Na and K) and the like.
- the positive electrode active material such as M 2 MnO 3 and MNi 0.5 Mn 1.5 O 2 is used when the secondary battery is operated at a voltage exceeding 4.4 V or a voltage of 4.6 V or higher. , It is preferable in that the crystal structure does not collapse.
- an electrochemical device such as a secondary battery using a positive electrode material containing a positive electrode active material exemplified above does not easily decrease its residual capacity, does not easily change its resistance increase rate, and has a high resistance even when stored at a high temperature. It is preferable because the battery performance does not deteriorate even if it is operated by a voltage.
- M 2 MnO 3 and MM 6 O 2 are at least one metal selected from the group consisting of Li, Na and K, and M 6 is Co, Ni. , Mn, Fe, and other transition metals) and solid solution materials.
- the solid solution material is, for example, an alkali metal manganese oxide represented by the general formula Mx [Mn (1-y) M 7 y ] Oz.
- M in the formula is at least one metal selected from the group consisting of Li, Na and K
- M 7 is composed of at least one metal element other than M and Mn, for example, Co, Ni. , Fe, Ti, Mo, W, Cr, Zr and Sn contains one or more elements selected from the group.
- the values of x, y, and z in the equation are in the range of 1 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, and 1.5 ⁇ z ⁇ 3.
- a manganese-containing solid solution material in which LiNiO 2 or LiCoO 2 is solid-dissolved based on Li 2 MnO 3 such as Li 1.2 Mn 0.5 Co 0.14 Ni 0.14 O 2 has a high energy density. It is preferable because it can provide an alkali metal ion secondary battery.
- lithium phosphate in the positive electrode active material because the continuous charging characteristics are improved.
- the use of lithium phosphate is not limited, it is preferable to use the above-mentioned positive electrode active material in combination with lithium phosphate.
- the lower limit of the amount of lithium phosphate used is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass, based on the total of the positive electrode active material and lithium phosphate. % Or more, and the upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less.
- Examples of the conductive polymer include a p-doping type conductive polymer and an n-doping type conductive polymer.
- Examples of the conductive polymer include polyacetylene-based, polyphenylene-based, heterocyclic polymers, ionic polymers, ladders, network-like polymers and the like.
- a substance having a composition different from that attached to the surface of the positive electrode active material may be used.
- Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide and other oxides, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and calcium sulfate.
- Sulfates such as aluminum sulfate
- carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate, carbon and the like.
- surface-adhering substances are, for example, dissolved or suspended in a solvent, impregnated with the positive electrode active material, or added, and then dried, or the surface-adhering substance precursor is dissolved or suspended in the solvent to activate the positive electrode. It can be attached to the surface of the positive electrode active material by a method of impregnating the substance and then reacting it by heating or the like, a method of adding it to the positive electrode active material precursor and firing it at the same time, or the like. In addition, when carbon is attached, a method of mechanically attaching carbonaceous material later in the form of activated carbon or the like can also be used.
- the amount of the surface adhering substance is preferably 0.1 ppm or more, more preferably 1 ppm or more, further preferably 10 ppm or more, and the upper limit is preferably 20% or less, more preferably 0.1 ppm or more, more preferably 1 ppm or more, more preferably 10 ppm or more, in terms of mass with respect to the positive electrode active material. Is used at 10% or less, more preferably 5% or less.
- the surface-adhering substance can suppress the oxidation reaction of the solid electrolyte on the surface of the positive electrode active material, and can improve the battery life. If the amount of adhesion is too small, the effect is not sufficiently exhibited, and if it is too large, resistance may increase because it inhibits the entry and exit of lithium ions.
- Examples of the shape of the particles of the positive electrode active material include lumps, polyhedra, spheres, elliptical spheres, plates, needles, and columns as conventionally used. Further, the primary particles may be aggregated to form secondary particles.
- the tap density of the positive electrode active material is preferably 0.5 g / cm 3 or more, more preferably 0.8 g / cm 3 or more, and further preferably 1.0 g / cm 3 or more.
- the tap density of the positive electrode active material is lower than the above lower limit, the amount of the dispersion medium required for forming the positive electrode active material layer increases, and the required amount of the conductive material and the binder increases, so that the positive electrode to the positive electrode active material layer is formed.
- the filling rate of the active material is restricted, and the battery capacity may be restricted.
- the tap density is the powder filling density (tap density) g / cm 3 when 5 to 10 g of positive electrode active material powder is placed in a 10 ml glass graduated cylinder and tapped 200 times with a stroke of about 20 mm. Ask as.
- the median diameter d50 (secondary particle diameter when the primary particles are aggregated to form secondary particles) of the particles of the positive electrode active material is preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferable. Is 0.8 ⁇ m or more, most preferably 1.0 ⁇ m or more, preferably 30 ⁇ m or less, more preferably 27 ⁇ m or less, still more preferably 25 ⁇ m or less, and most preferably 22 ⁇ m or less. If it is below the above lower limit, it may not be possible to obtain a high tap density product, and if it exceeds the upper limit, it takes time to diffuse lithium in the particles, resulting in deterioration of battery performance or making a positive electrode for the battery, that is, an active material.
- the median diameter d50 is measured by a known laser diffraction / scattering type particle size distribution measuring device.
- LA-920 manufactured by HORIBA is used as the particle size distribution meter
- a 0.1 mass% sodium hexametaphosphate aqueous solution is used as the dispersion medium used for the measurement, and the measured refractive index is set to 1.24 after ultrasonic dispersion for 5 minutes. Is measured.
- the average primary particle diameter of the positive electrode active material is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, still more preferably 0. It is 2 ⁇ m or more, and the upper limit is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less, still more preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. If it exceeds the above upper limit, it is difficult to form spherical secondary particles, which adversely affects the powder filling property and greatly reduces the specific surface area, so that there is a high possibility that the battery performance such as output characteristics will deteriorate. In some cases. On the contrary, if it is less than the above lower limit, problems such as inferior reversibility of charge / discharge may occur because the crystal is usually underdeveloped.
- the average primary particle size of the positive electrode active material is measured by observation using a scanning electron microscope (SEM). Specifically, in a photograph with a magnification of 10000 times, the longest value of the intercept by the left and right boundary lines of the primary particles with respect to the horizontal straight line is obtained for any 50 primary particles, and the average value is taken. Be done.
- the BET specific surface area of the positive electrode active material is preferably 0.1 m 2 / g or more, more preferably 0.2 m 2 / g or more, still more preferably 0.3 m 2 / g or more, and the upper limit is preferably 50 m 2 / g. It is g or less, more preferably 40 m 2 / g or less, still more preferably 30 m 2 / g or less. If the BET specific surface area is smaller than this range, the battery performance tends to deteriorate, and if it is large, the tap density does not easily increase, and a problem may easily occur in the coatability at the time of forming the positive electrode active material layer.
- the BET specific surface area is large after pre-drying the sample at 150 ° C. for 30 minutes under nitrogen flow using a surface area meter (for example, a fully automatic surface area measuring device manufactured by Okura Riken Co., Ltd.). It is defined by the value measured by the nitrogen adsorption BET 1-point method by the gas flow method using a nitrogen helium mixed gas accurately adjusted so that the value of the relative pressure of nitrogen with respect to the pressure is 0.3.
- the particles of the positive electrode active material are mainly secondary particles.
- the particles of the positive electrode active material preferably contain 0.5 to 7.0% by volume of fine particles having an average particle size of secondary particles of 40 ⁇ m or less and an average primary particle size of 1 ⁇ m or less.
- a general method is used as a method for producing an inorganic compound.
- various methods can be considered for producing a spherical or elliptical spherical active material.
- a raw material for a transition metal is dissolved or pulverized and dispersed in a solvent such as water, and the pH is adjusted while stirring.
- a method of obtaining an active material by preparing and recovering a spherical precursor, drying the precursor as necessary, adding a Li source such as LiOH, Li 2 CO 3 , or LiNO 3 and firing at a high temperature can be mentioned. ..
- the positive electrode active material may be used alone, or two or more kinds having different compositions may be used in any combination or ratio.
- Preferred combinations in this case include a combination of LiCoO 2 and a ternary system such as LiNi 0.33 Co 0.33 Mn 0.33 O 2 , LiCoO 2 and LiMn 2 O 4 or a part of this Mn. Examples thereof include a combination with a transition metal or the like, or a combination with LiFePO 4 and LiCoO 2 or a part of the Co replaced with another transition metal or the like.
- the content of the positive electrode active material is preferably 50 to 99.5% by mass, more preferably 80 to 99% by mass in the positive electrode mixture in terms of high battery capacity.
- the content of the positive electrode active material is preferably 80% by mass or more, more preferably 82% by mass or more, and particularly preferably 84% by mass or more.
- the upper limit is preferably 99% by mass or less, more preferably 98% by mass or less. If the content of the positive electrode active material in the positive electrode mixture is low, the electric capacity may be insufficient. On the contrary, if the content is too high, the strength of the positive electrode may be insufficient.
- the negative electrode active material is not particularly limited, and for example, lithium metal, artificial graphite, graphite carbon fiber, resin calcined carbon, thermally decomposed gas phase growth carbon, coke, mesocarbon microbeads (MCMB), and full frill alcohol resin calcined carbon.
- MCMB mesocarbon microbeads
- the content of the negative electrode active material is preferably 40% by mass or more, more preferably 50% by mass in the all-solid-state secondary battery mixture sheet in order to increase the capacity of the obtained all-solid-state secondary battery mixture sheet. As mentioned above, it is particularly preferably 60% by mass or more.
- the upper limit is preferably 99% by mass or less, more preferably 98% by mass or less.
- a known conductive material can be arbitrarily used. Specific examples include metal materials such as copper and nickel, natural graphite, graphite such as artificial graphite (graphite), acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and other carbon black, and needle coke. , Carbon nanotubes, fullerene, carbon materials such as amorphous carbon such as VGCF, and the like. It should be noted that one of these may be used alone, or two or more of them may be used in any combination and ratio.
- the conductive auxiliary agent is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and usually 50% by mass or less, preferably 50% by mass or more in the electrode active material layer. Is used so as to contain 30% by mass or less, more preferably 15% by mass or less. If the content is lower than this range, the conductivity may be insufficient. On the contrary, if the content is higher than this range, the battery capacity may decrease.
- the all-solid-state secondary battery mixture sheet may further contain a thermoplastic resin.
- thermoplastic resin include vinylidene fluoride, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polyethylene oxide and the like. One type may be used alone, or two or more types may be used in any combination and ratio.
- the ratio of the thermoplastic resin to the electrode active material is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and usually 3.0% by mass or less. It is preferably in the range of 2.5% by mass or less, more preferably 2.0% by mass or less.
- the content of the binder is usually 0.1% by mass or more, preferably 0.1% by mass or more, as the ratio of the binder in the all-solid-state secondary battery mixture sheet. 0.3% by mass or more, more preferably 0.5% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, still more preferably 40% by mass or less, and most preferably 20% by mass or less. be. If the proportion of the binder is too low, the active material cannot be sufficiently retained in the all-solid-state secondary battery mixture sheet, and the mechanical strength of the all-solid-state secondary battery mixture sheet becomes insufficient, resulting in cycle characteristics and the like. It may deteriorate the battery performance. On the other hand, if it is too high, it may lead to a decrease in battery capacity and conductivity.
- the manufacturing method of the all-solid-state secondary battery mixture sheet of the present disclosure is not limited, but an example of a specific manufacturing method is shown below.
- the all-solid-state secondary battery mixture sheet disclosed in the present disclosure is: Step of applying shearing force while mixing a raw material composition containing a solid electrolyte and a binder (1) A sheet for forming the bulk-shaped all-solid-state secondary battery mixture obtained in the step (1) into a bulk shape and the bulk-shaped all-solid-state secondary battery mixture obtained in the step (2). Step of rolling into a shape (3) It can be obtained by a method for manufacturing an electrode mixture sheet for a secondary battery having the above.
- the obtained mixture for the all-solid secondary battery was determined only by the solid electrolyte, the binder and the like. It exists in a formless state.
- Specific mixing methods include W-type mixer, V-type mixer, drum-type mixer, ribbon mixer, conical screw-type mixer, single-screw kneader, double-screw kneader, mix muller, stirring mixer, and planeta.
- a method of mixing using a Lee mixer or the like can be mentioned.
- the mixing conditions may be appropriately set to the rotation speed and the mixing time.
- the rotation speed is preferably 1000 rpm or less. It is preferably in the range of 10 rpm or more, more preferably 15 rpm or more, still more preferably 20 rpm or more, and preferably 900 rpm or less, more preferably 800 rpm or less, still more preferably 700 rpm. Below the above range, mixing will take longer and productivity will be affected. On the other hand, if it exceeds the limit, fibrillation may proceed excessively, resulting in an electrode mixture sheet having inferior strength.
- molding into a bulk means that the all-solid-state secondary battery mixture is made into one lump.
- Specific methods for forming into a bulk form include extrusion molding and press molding.
- the "bulk shape" is not particularly specified in shape, and may be in a state of one lump, and includes a rod shape, a sheet shape, a spherical shape, a cube shape, and the like.
- the size of the mass is preferably 10,000 ⁇ m or more in diameter or the smallest side of the cross section. More preferably, it is 20000 ⁇ m or more.
- Specific examples of the rolling method in the above step (3) include a method of rolling using a roll press machine, a flat plate press machine, a calender roll machine, or the like.
- the number of steps (4) is preferably 2 times or more and 10 times or less, and more preferably 3 times or more and 9 times or less.
- Specific examples of the rolling method include a method of rotating two or a plurality of rolls and passing a rolled sheet between them to form a thinner sheet.
- the rolled sheet may be roughly crushed, then molded into a bulk shape again, and rolled into a sheet shape (5).
- the number of steps (5) is preferably 1 or more and 12 times or less, and more preferably 2 or more and 11 times or less.
- step (5) specific methods for coarsely crushing the rolled sheet and forming it into a bulk form include a method of folding the rolled sheet, a method of forming it into a rod or a thin film sheet, and a method of forming chips.
- coarse crushing means changing the form of the rolled sheet obtained in step (3) or step (4) to another form in order to roll into a sheet in the next step. This includes cases where the rolled sheet is simply folded.
- step (4) may be performed after the step (5), or may be repeated. Further, uniaxial stretching or biaxial stretching may be performed in steps (2) to (3), (4) and (5). Further, the fibril diameter (median value) can be adjusted by the degree of coarse crushing in the step (5).
- the rolling ratio is preferably 10% or more, more preferably 20% or more, preferably 80% or less, more preferably 65% or less, and further. It is preferably in the range of 50% or less. If it falls below the above range, it takes time as the number of rolling times increases, which affects productivity. On the other hand, if it exceeds the limit, fibrillation may proceed excessively, resulting in an electrode mixture sheet having poor strength and flexibility.
- the rolling ratio here refers to the reduction rate of the thickness after processing with respect to the thickness of the sample before rolling.
- the sample before rolling may be a bulk-shaped raw material composition or a sheet-shaped raw material composition.
- the thickness of the sample refers to the thickness in the direction in which a load is applied during rolling.
- the PTFE powder is fibrillated by applying a shearing force.
- excessive shear stress may promote fibril formation too much and impair flexibility.
- weak shear stress may not be sufficient in terms of strength.
- the fibril diameter (median value) is achieved by performing the steps of applying shear stress to the appropriate PTFE during mixing and rolling to promote fibrillation, rolling the resin and rolling it into a sheet shape.
- the all-solid-state secondary battery mixture sheet of the present disclosure may be either a positive electrode sheet or a negative electrode sheet.
- the positive electrode active material or the negative electrode active material may be mixed together with the solid electrolyte and the binder. ..
- the positive electrode is composed of a current collector and the positive electrode sheet.
- the material of the current collector for the positive electrode include metals such as aluminum, titanium, tantalum, stainless steel and nickel, or metal materials such as alloys thereof; carbon materials such as carbon cloth and carbon paper. Of these, metal materials, especially aluminum or alloys thereof, are preferable.
- Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, expanded metal, punch metal, foamed metal, etc. in the case of metal material, and carbon plate, carbon thin film, carbon in the case of carbon material. Examples include columns. Of these, metal foil is preferable.
- the metal foil may be appropriately formed in a mesh shape.
- the thickness of the metal foil is arbitrary, but is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If the metal foil is thinner than this range, the strength required for the current collector may be insufficient. On the contrary, if the metal foil is thicker than this range, the handleability may be impaired.
- the conductive auxiliary agent is applied to the surface of the current collector from the viewpoint of reducing the electric contact resistance between the current collector and the positive electrode mixture sheet.
- the conductive auxiliary agent include carbon and precious metals such as gold, platinum and silver.
- the positive electrode may be manufactured by a conventional method. For example, a method of laminating the positive electrode sheet and the current collector via an adhesive and drying the sheet can be mentioned.
- the density of the positive electrode sheet is preferably 2.0 g / cm 3 or more, more preferably 2.1 g / cm 3 or more, still more preferably 2.3 g / cm 3 or more, and preferably 4.0 g / cm.
- the range is 3 or less, more preferably 3.9 g / cm 3 or less, still more preferably 3.8 g / cm 3 or less. If it exceeds this range, the conductivity between the active materials decreases, the battery resistance increases, and high output may not be obtained. If it is lower than that, the content of the active material that is hard and fragile is low, and the battery may have a low capacity.
- the thickness of the positive electrode is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the mixture sheet minus the thickness of the current collector is preferably 10 ⁇ m as the lower limit with respect to one side of the current collector. As described above, it is more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, and more preferably 450 ⁇ m or less.
- a substance having a different composition attached to the surface of the positive electrode may be used.
- Surface adhering substances include aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, bismuth oxide and other oxides, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate and calcium sulfate.
- Sulfates such as aluminum sulfate
- carbonates such as lithium carbonate, calcium carbonate, magnesium carbonate, carbon and the like.
- the negative electrode is composed of a current collector and the negative electrode sheet.
- the material of the current collector for the negative electrode include metals such as copper, nickel, titanium, tantalum, and stainless steel, or metal materials such as alloys thereof; carbon materials such as carbon cloth and carbon paper. Of these, metal materials, especially copper, nickel, or alloys thereof are preferable.
- Examples of the shape of the current collector include metal foil, metal cylinder, metal coil, metal plate, expanded metal, punch metal, foamed metal, etc. in the case of metal material, and carbon plate, carbon thin film, carbon in the case of carbon material. Examples include columns. Of these, metal foil is preferable.
- the metal foil may be appropriately formed in a mesh shape.
- the thickness of the metal foil is arbitrary, but is usually 1 ⁇ m or more, preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and usually 1 mm or less, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less. If the metal foil is thinner than this range, the strength required for the current collector may be insufficient. On the contrary, if the metal foil is thicker than this range, the handleability may be impaired.
- the negative electrode may be manufactured by a conventional method. For example, a method of laminating the negative electrode sheet and the current collector via an adhesive and drying the sheet can be mentioned.
- the density of the negative electrode sheet is preferably 1.3 g / cm 3 or more, more preferably 1.4 g / cm 3 or more, still more preferably 1.5 g / cm 3 or more, and preferably 2.0 g / cm.
- the range is 3 or less, more preferably 1.9 g / cm 3 or less, still more preferably 1.8 g / cm 3 or less. If it exceeds this range, the permeability of the solid electrolyte to the vicinity of the interface between the current collector and the active material is lowered, and the charge / discharge characteristics particularly at a high current density are lowered, and high output may not be obtained. If it is lower than that, the conductivity between active materials decreases, the battery resistance increases, and high output may not be obtained.
- the thickness of the negative electrode is not particularly limited, but from the viewpoint of high capacity and high output, the thickness of the mixture sheet obtained by subtracting the metal leaf thickness of the current collector is preferable as the lower limit with respect to one side of the current collector. Is 10 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, and more preferably 450 ⁇ m or less.
- the present disclosure is also an all-solid-state secondary battery using the above-mentioned mixture sheet for an all-solid-state secondary battery.
- the all-solid-state secondary battery is preferably a lithium-ion battery. Further, the all-solid-state secondary battery is preferably a sulfide-based all-solid-state secondary battery.
- the all-solid secondary battery of the present disclosure is an all-solid secondary battery including a positive electrode, a negative electrode, and a solid electrolyte layer interposed between the positive electrode and the negative electrode, and the positive electrode, the negative electrode, and the solid electrolyte layer are described above.
- the all-solid-state secondary battery of the present disclosure may use a positive electrode, a negative electrode, and a part of the solid electrolyte layer that are not the mixture sheet for the all-solid-state secondary battery of the present disclosure.
- the laminated structure of the all-solid-state secondary battery includes a positive electrode having a positive electrode sheet and a positive electrode current collector, a negative electrode having a negative electrode sheet and a negative electrode current collector, and sulfide sandwiched between the positive electrode and the negative electrode.
- a system solid electrolyte layer is provided.
- the all-solid-state secondary battery of the present disclosure may include a separator between the positive electrode and the negative electrode.
- the separator include a porous film such as polyethylene and polypropylene; a non-woven fabric made of a resin such as polypropylene, and a non-woven fabric such as a glass fiber non-woven fabric.
- the all-solid-state secondary battery of the present disclosure may further include a battery case.
- the shape of the battery case used in the present disclosure is not particularly limited as long as it can accommodate the above-mentioned positive electrode, negative electrode, electrolyte layer for sulfide-based solid-state battery, etc., but specifically, it is a cylindrical type. , Square type, coin type, laminated type and the like.
- the positive electrode, the solid electrolyte layer sheet, and the negative electrode may be laminated in this order and pressed to obtain an all-solid-state secondary battery.
- the all-solid-state secondary battery mixture sheet of the present disclosure it is possible to manufacture an all-solid-state secondary battery with a small amount of water in the system, and the all-solid-state secondary battery has good performance. Can be and is suitable.
- aqueous dispersion (solid content 31.2% by mass) was obtained.
- the obtained aqueous polytetrafluoroethylene dispersion was diluted to a solid content concentration of 15% and gently stirred in a container equipped with a stirrer in the presence of nitric acid to solidify the polytetrafluoroethylene.
- the solidified polytetrafluoroethylene was separated and dried at 160 ° C. for 18 hours to obtain powdered PTFE-1.
- Example 1 A sulfide-based solid electrolyte (0.75Li 2 S / 0.25P 2 S 5 ) and powdered PTFE-1 were weighed and stirred in a mortar at 200 rpm for 1 hour to obtain a mixture.
- the powdered PTFE-1 was dried in a vacuum dryer at 50 ° C. for 1 hour before use.
- the powdered PTFE was previously sifted using a stainless steel sieve having an opening of 500 ⁇ m, and the one remaining on the sieve was used.
- the obtained mixture was formed into a bulk shape and rolled into a sheet shape.
- the rolled sheet obtained earlier is roughly crushed by folding it in two, formed into a bulk shape again, and then rolled into a sheet shape using a metal roll on a flat plate to form fibril.
- the process of accelerating was repeated four times.
- it was further rolled to obtain a sheet-like solid electrolyte layer having a thickness of 500 ⁇ m.
- a sheet-shaped solid electrolyte layer was cut out and put into a press machine for rolling.
- a load of 5 kN was repeatedly applied to adjust the thickness.
- the gap was adjusted so that the thickness of the final solid electrolyte layer was 150 ⁇ m.
- the above work was performed in an Ar glove box (dew point of about ⁇ 80 ° C.).
- the initial rolling rate was the highest at 39%.
- Example 2 The powdered PTFE shown in Table 2 was used for each, and a solid electrolyte layer was prepared in the same manner as in Example 1 except for the above.
- Example 5 A solid electrolyte layer was prepared in the same manner as in Example 1 except that the powdered PTFE shown in Table 2 was used without sieving.
- the process of accelerating was repeated four times. Then, it was further rolled to obtain a sheet-like solid electrolyte layer having a thickness of 500 ⁇ m. Further, a sheet-shaped solid electrolyte layer was cut out and put into a press machine for rolling. Further, a load of 8 kN was repeatedly applied to adjust the thickness. The gap was adjusted so that the thickness of the final solid electrolyte layer was 150 ⁇ m.
- the above work was performed in an Ar glove box (dew point of about ⁇ 80 ° C.). The initial rolling rate was the largest at 61%.
- Comparative Example 2 A sheet-shaped solid electrolyte layer was prepared using the powdered PTFE shown in Table 2 in the same manner as in Comparative Example 1 except for the above.
- a binder of VDF: HFP copolymer was prepared, this was added to butyl butyrate (manufactured by Kishida Chemical Co., Ltd.), and the mixture was stirred with a mix rotor to prepare a binder solution.
- the entire binder solution was set to 100% by mass, and 5% by mass of the binder was contained.
- a sulfide-based solid electrolyte (0.75Li 2 S / 0.25P 2 S 5 ) to the binder solution and performing ultrasonic treatment using an ultrasonic homogenizer, the sulfide-based solid electrolyte and the binder can be obtained.
- a "slurry for a solid electrolyte layer" was obtained.
- the prepared electrolyte slurry was applied onto a peelable substrate using a doctor blade and dried. Then, a press was performed, and the press was performed so as to have the same density as in Example 1 to prepare solid electrolyte pellets. The above work was performed in an Ar glove box (dew point of about ⁇ 80 ° C.).
- PTFE fibril diameter (median) [PTFE fibril diameter (median)] (1) Using a scanning electron microscope (S-4800 type manufactured by Hitachi, Ltd.), a magnified photograph (7000 times) of the sheet-like solid electrolyte layer is taken to obtain an image. (2) Draw two lines horizontally at equal intervals on this image and divide the image into three equal parts. (3) For all the PTFE fibers on the upper straight line, the diameters of three points per PTFE fiber are measured, and the average value is taken as the diameter of the PTFE fiber. For the three points to be measured, select the intersection of the PTFE fiber and the straight line, and the location shifted by 0.5 ⁇ m above and below the intersection. (Excluding unfibered PTFE primary particles).
- the prepared solid electrolyte sheet was cut into 2 cm in length and 6 cm in width and used as a test piece. After winding around a round bar having a diameter of 4 mm, the test piece was visually confirmed and evaluated according to the following criteria. When no scratches or cracks were confirmed, it was evaluated as ⁇ , and when cracks were confirmed, it was evaluated as ⁇ .
- the sheet-shaped solid electrolyte layer of the example was excellent in physical properties.
- the all-solid-state secondary battery mixture of the present disclosure and the all-solid-state secondary battery mixture sheet containing the same can be used for manufacturing an all-solid-state secondary battery.
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
また、本開示は、微細な繊維構造を有するポリテトラフルオロエチレン樹脂を含有する全固体二次電池用シートを製造する方法を提供することを目的とする。
結着剤は、ポリテトラフルオロエチレン樹脂であり、
ポリテトラルオロエチレン樹脂は、フィブリル径(中央値)が70nm以下の繊維状構造を有することを特徴とする全固体二次電池用合剤である。
上記全固体二次電池用合剤は、硫化物系全固体二次電池用であることが好ましい。
上記原料組成物は、実質的に液体媒体を含有しないことが好ましい。
上記粉末状のポリテトラフルオロエチレン樹脂は、標準比重が2.11~2.20であることが好ましい。
上記粉末状のポリテトラフルオロエチレン樹脂は、二次粒子径が500μm以上のポリテトラフルオロエチレン樹脂を80質量%以上含むことが好ましい。
前記工程(1)によって得られた全固体二次電池用合剤をバルク状に成形する工程(2)及び
前記工程(2)によって得られたバルク状の全固体二次電池用合剤をシート状に圧延する工程(3)
を有する全固体二次電池用合剤シートの製造方法であって、結着剤は、粉末状のポリテトラフルオロエチレン樹脂であることを特徴とする全固体二次電池用合剤シートの製造方法でもある。
本開示は、全固体二次電池において好適に使用することができる全固体二次電池用合剤及びこれを含有する合剤シートを提供する。
本開示の全固体二次電池用合剤及びこれを含有する合剤シートにおいては、PTFEを結着剤として使用するものである。従来の全固体二次電池用合剤においては、ビニリデンフルオライドとヘキサフルオロプロピレンとの共重合体等の、溶媒に溶解する樹脂を結着剤として使用し、これを含有するスラリーの塗布・乾燥によって、全固体二次電池用合剤を作成する方法が一般的であった。
(1)走査型電子顕微鏡(S-4800型 日立製作所製)を用いて、全固体二次電池用合剤シートの拡大写真(7000倍)を撮影し画像を得る。
(2)この画像に水平方向に等間隔で2本の線を引き、画像を三等分する。
(3)上方の直線上にある全てのPTFE繊維について、PTFE繊維1本あたり3箇所の直径を測定し、平均した値を当該PTFE繊維の直径とする。測定する3箇所は、PTFE繊維と直線との交点、交点からそれぞれ上下に0.5μmずつずらした場所を選択する。(未繊維化のPTFE一次粒子は除く)。
(4)上記(3)の作業を、下方の直線上にある全てのPTFE繊維に対して行う。
(5)1枚目の画像を起点に画面右方向に1mm移動し、再度撮影を行い、上記(3)及び(4)によりPTFE繊維の直径を測定する。これを繰り返し、測定した繊維数が80本を超えた時点で終了とする。
(6)上記測定した全てのPTFE繊維の直径の中央値をフィブリル径の大きさとした。
固体電解質及び結着剤を含む原料組成物を混合しながら、剪断力を付与する工程(1)
前記工程(1)によって得られた全固体二次電池用合剤をバルク状に成形する工程(2)及び
前記工程(2)によって得られたバルク状の全固体二次電池用合剤をシート状に圧延する工程(3)によって行う方法を挙げることができる。
また、工程(3)又は工程(4)のあとに、得られた圧延シートを粗砕したのち再度バルク状に成形し、シート状に圧延する工程(5)を有することによってもフィブリル径を調整することができる。工程(5)は、例えば1回以上12回以下繰り返すことが好ましい。
共重合体の場合、コモノマーであるフッ素原子含有モノマーとしては、クロロトリフルオロエチレン、ヘキサフルオロプロピレン、フルオロアルキルエチレン、パーフルオロアルキルエチレン、フルオロアルキル・フルオロビニルエーテル等を挙げることができる。
水分含有量が500ppm以下であることによって、固体電解質の劣化を低減させるという点で好ましい。
上記水分含有量は、300ppm以下であることが更に好ましい。
二次粒子径が500μm以上のPTFEを用いることで、より抵抗が低く、靭性に富んだ合剤シートを得ることができる。
PTFEの平均一次粒子径が大きいほど、その粉末を用いて押出成形をする際に、押出圧力の上昇を抑えられ、成形性にも優れる。上限は特に限定されないが500nmであってよい。重合工程における生産性の観点からは、350nmであることが好ましい。
具体例として、例えば、Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2、Li2O-Al2O3-SiO2-P2O5-TiO2等が挙げられる。
結晶構造を有する酸化物としては、ペロブスカイト型(La0.51Li0.34TiO2.94など)、NASICON型(Li1.3Al0.3Ti1.7(PO4)3など)、ガーネット型(Li7La3Zr2O12(LLZ)など)等が挙げられる。なかでも、NASICON型が好ましい。
また、硫化物系全固体二次電池に好適である。
本開示の全固体二次電池用合剤は、全固体二次電池に使用するにあたっては、通常、シート状の形態で使用される。
本開示の全固体二次電池用合剤シートを正極用シートとして使用する場合、全固体二次電池用合剤シートには正極活物質を配合する。上記正極活物質は、固体電池の正極活物質として公知の正極活物質を適用可能である。特に、リチウムイオンを吸蔵・放出可能な正極活物質を用いることが好ましい。
上記正極活物質としては、電気化学的にアルカリ金属イオンを吸蔵・放出可能なものであれば特に制限されないが、例えば、アルカリ金属と少なくとも1種の遷移金属を含有する物質が好ましい。具体例としては、アルカリ金属含有遷移金属複合酸化物、アルカリ金属含有遷移金属リン酸化合物、導電性高分子等が挙げられる。
なかでも、正極活物質としては、特に、高電圧を産み出すアルカリ金属含有遷移金属複合酸化物が好ましい。上記アルカリ金属イオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオン等が挙げられる。好ましい態様において、アルカリ金属イオンは、リチウムイオンであり得る。即ち、この態様において、アルカリ金属イオン二次電池は、リチウムイオン二次電池である。
式:MaMn2-bM1 bO4
(式中、Mは、Li、Na及びKからなる群より選択される少なくとも1種の金属であり;0.9≦a;0≦b≦1.5;M1はFe、Co、Ni、Cu、Zn、Al、Sn、Cr、V、Ti、Mg、Ca、Sr、B、Ga、In、SiおよびGeよりなる群より選択される少なくとも1種の金属)で表されるアルカリ金属・マンガンスピネル複合酸化物、
式:MNi1-cM2cO2
(式中、Mは、Li、Na及びKからなる群より選択される少なくとも1種の金属であり;0≦c≦0.5;M2はFe、Co、Mn、Cu、Zn、Al、Sn、Cr、V、Ti、Mg、Ca、Sr、B、Ga、In、SiおよびGeよりなる群より選択される少なくとも1種の金属)で表されるアルカリ金属・ニッケル複合酸化物、または、
式:MCo1-dM3 dO2
(式中、Mは、Li、Na及びKからなる群より選択される少なくとも1種の金属であり;0≦d≦0.5;M3はFe、Ni、Mn、Cu、Zn、Al、Sn、Cr、V、Ti、Mg、Ca、Sr、B、Ga、In、SiおよびGeよりなる群より選択される少なくとも1種の金属)
で表されるアルカリ金属・コバルト複合酸化物が挙げられる。上記において、Mは、好ましくは、Li、Na及びKからなる群より選択される1種の金属であり、より好ましくはLiまたはNaであり、さらに好ましくはLiである。
MNihCoiMnjM5 kO2 (3)
(式中、Mは、Li、Na及びKからなる群より選択される少なくとも1種の金属であり、M5はFe、Cu、Zn、Al、Sn、Cr、V、Ti、Mg、Ca、Sr、B、Ga、In、Si及びGeからなる群より選択される少なくとも1種を示し、(h+i+j+k)=1.0、0≦h≦1.0、0≦i≦1.0、0≦j≦1.5、0≦k≦0.2である。)
MeM4 f(PO4)g (4)
(式中、Mは、Li、Na及びKからなる群より選択される少なくとも1種の金属であり、M4はV、Ti、Cr、Mn、Fe、Co、Ni及びCuからなる群より選択される少なくとも1種を示し、0.5≦e≦3、1≦f≦2、1≦g≦3)で表される化合物が挙げられる。上記において、Mは、好ましくは、Li、Na及びKからなる群より選択される1種の金属であり、より好ましくはLiまたはNaであり、さらに好ましくはLiである。
上記リチウム含有遷移金属リン酸化合物としては、オリビン型構造を有するものが好ましい。
場合がある。
なお、本開示では、タップ密度は、正極活物質粉体5~10gを10mlのガラス製メスシリンダーに入れ、ストローク約20mmで200回タップした時の粉体充填密度(タップ密度)g/cm3として求める。
上記正極活物質の粒子は、二次粒子の平均粒子径が40μm以下で、かつ、平均一次粒子径が1μm以下の微粒子を、0.5~7.0体積%含むものであることが好ましい。平均一次粒子径が1μm以下の微粒子を含有させることにより、固体電解質との接触面積が大きくなり、全固体二次電池用シートと固体電解質との間でのリチウムイオンの拡散をより速くすることができ、その結果、電池の出力性能を向上させることができる。
また、正極活物質の含有量は、好ましくは80質量%以上、より好ましくは82質量%以上、特に好ましくは84質量%以上である。また上限は、好ましくは99質量%以下、より好ましくは98質量%以下である。正極合剤中の正極活物質の含有量が低いと電気容量が不十分となる場合がある。逆に含有量が高すぎると正極の強度が不足する場合がある。
上記導電助剤としては、公知の導電材を任意に用いることができる。具体例としては、銅、ニッケル等の金属材料、天然黒鉛、人造黒鉛等の黒鉛(グラファイト)、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等のカーボンブラック、ニードルコークス、カーボンナノチューブ、フラーレン、VGCF等の無定形炭素等の炭素材料等が挙げられる。なお、これらは、1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。
全固体二次電池用合剤シートは、更に、熱可塑性樹脂を含んでいてもよい。
熱可塑性樹脂としては、フッ化ビニリデンや、ポリプロピレン、ポリエチレン、ポリスチレン、ポリエチレンテレフタレート、ポリエチレンオキシドなどが挙げられる。1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用してもよい。
本開示の全固体二次電池用合剤シートは、その製造方法を限定されるものではないが、以下に具体的な製造方法の一例を示す。
本開示の全固体二次電池用合剤シートは、
固体電解質及び結着剤を含む原料組成物を混合しながら、剪断力を付与する工程(1)
前記工程(1)によって得られた全固体二次電池用合剤をバルク状に成形する工程(2)及び
前記工程(2)によって得られたバルク状の全固体二次電池用合剤をシート状に圧延する工程(3)
を有する二次電池用電極合剤シートの製造方法によって得ることができる。
バルク状に成形する具体的な方法として、押出成形、プレス成形などが挙げられる。
また、「バルク状」とは、特に形状が特定されるものではなく、1つの塊状になっている状態であればよく、ロッド状、シート状、球状、キューブ状等の形態が含まれる。上記塊の大きさは、その断面の直径または最小の一辺が10000μm以上であることが好ましい。より好ましくは20000μm以上である。
工程(4)の回数としては、2回以上10回以下が好ましく、3回以上9回以下がより好ましい。
具体的な圧延方法としては、例えば、2つあるいは複数のロールを回転させ、その間に圧延シートを通すことによって、より薄いシート状に加工する方法等が挙げられる。
また、工程(2)ないし、(3)、(4)、(5)において1軸延伸もしくは2軸延伸を行っても良い。
また、工程(5)での粗砕程度によってもフィブリル径(中央値)を調整することができる。
なお、ここでいう圧延率とは、試料の圧延加工前の厚みに対する加工後の厚みの減少率を指す。圧延前の試料は、バルク状の原料組成物であっても、シート状の原料組成物であってもよい。試料の厚みとは、圧延時に荷重をかける方向の厚みを指す。
(正極)
本開示において、正極は、集電体と、上記正極用シートとから構成されることが好適である。
正極用集電体の材質としては、アルミニウム、チタン、タンタル、ステンレス鋼、ニッケル等の金属、又は、その合金等の金属材料;カーボンクロス、カーボンペーパー等の炭素材料が挙げられる。なかでも、金属材料、特にアルミニウム又はその合金が好ましい。
金属箔の厚さは任意であるが、通常1μm以上、好ましくは3μm以上、より好ましくは5μm以上、また、通常1mm以下、好ましくは100μm以下、より好ましくは50μm以下である。金属箔がこの範囲よりも薄いと集電体として必要な強度が不足する場合がある。逆に、金属箔がこの範囲よりも厚いと取り扱い性が損なわれる場合がある。
本開示において、負極は、集電体と、上記負極用シートとから構成されることが好適である。
負極用集電体の材質としては、銅、ニッケル、チタン、タンタル、ステンレス鋼等の金属、又は、その合金等の金属材料;カーボンクロス、カーボンペーパー等の炭素材料が挙げられる。なかでも、金属材料、特に銅、ニッケル、又はその合金が好ましい。
本開示は、上記全固体二次電池用合剤シートを用いた全固体二次電池でもある。
当該全固体二次電池は、リチウムイオン電池であることが好ましい。また、当該全固体二次電池は、硫化物系全固体二次電池であることが好ましい。
本開示の全固体二次電池は、正極、負極、並びに、当該正極及び当該負極の間に介在する固体電解質層を備える全固体二次電池であって、正極、負極及び固体電解質層に、上述した本開示の全固体二次電池用合剤シートである、正極用シート、負極用シート、又は固体電解質層シートを含有するものである。なお、本開示の全固体二次電池は、正極、負極及び固体電解質層の一部に、本開示の全固体二次電池用合剤シートでないものを用いるものであっても良い。
以下、本開示に係る全固体二次電池に用いられるセパレータ及び電池ケースについて、詳細に説明する。
本開示の全固体二次電池は、正極及び負極の間にセパレータを備えていてもよい。上記セパレータとしては、例えばポリエチレン、ポリプロピレン等の多孔膜;及びポリプロピレン等の樹脂製の不織布、ガラス繊維不織布等の不織布等を挙げることができる。
本開示の全固体二次電池は、さらに電池ケースを備えていてもよい。本開示に用いられる電池ケースの形状としては、上述した正極、負極、硫化物系固体電池用電解質層等を収納できるものであれば特に限定されるものではないが、具体的には、円筒型、角型、コイン型、ラミネート型等を挙げることができる。
本開示の全固体二次電池用合剤シートを使用することにより、系内の水分が少ない状態で全固体二次電池の製造を行うことができ、良好な性能を有する全固体二次電池とすることができ、好適である。
以下の実施例においては特に言及しない場合は、「部」「%」はそれぞれ「質量部」「質量%」を表す。
重合開始からTFEが367g(TFEの全重合量1032gに対して35.6質量%)消費された時点で、ラジカル捕捉剤としてヒドロキノン12.0mgを水20mlに溶解した水溶液をTFEで圧入した(水性媒体に対して濃度4.0ppm)。重合はその後も継続し、TFEの重合量が重合開始から1000gになった時点でTFEの供給を止め、直ちに系内のガスを放出して常圧とし、重合反応を終了してポリテトラフルオロエチレン水性分散体(固形分31.2質量%)を得た。得られたポリテトラフルオロエチレン水性分散体を固形分濃度15%まで希釈し、攪拌機付き容器内で硝酸の存在下において静かに、攪拌しポリテトラフルオロエチレンを凝固させた。凝固したポリテトラフルオロエチレンを分離し、160℃において18時間乾燥し、粉末状のPTFE-1を得た。
国際公開第2015‐080291号の作成例3を参考にして、粉末状のPTFE-2を作製した。
国際公開第2012/086710号の作製例1を参考にして、粉末状のPTFE-3を作製した。
国際第2012‐063622号の調整例1を参考にして、粉末状のPTFE-4を作製した。
作製したPTFEの物性表を表1に示す。
硫化物系固体電解質(0.75Li2S・0.25P2S5)と粉末状PTFE-1を秤量し、乳鉢にて200rpmで1時間撹拌し混合物を得た。
なお、粉末状のPTFE-1は真空乾燥機にて50℃、1時間乾燥して用いた。粉末状PTFEは事前に、目開き500μmのステンレスふるいを用いてふるいにかけ、ふるい上に残ったものを用いた。固形分は質量比で固体電解質:結着剤=95:5となるようにした。
得られた混合物をバルク状に成形し、シート状に圧延した。
その後、先程得られた圧延シートを2つに折りたたむことにより粗砕して、再度バルク状に成形した後、平らな板の上で金属ロールを用いてシート状に圧延することで、フィブリル化を促進させる工程を四度繰り返した。その後、更に圧延することで、厚さ500μmのシート状固体電解質層を得た。さらに、シート状固体電解質層を切り出し、プレス機に投入し圧延をおこなった。さらに、5kNの荷重を繰り返しかけて厚みを調整した。最終的な固体電解質層の厚みは150μmになるようにギャップを調整した。なお、上記作業はArグローボックス内(露点約-80℃)で行った。初回の圧延率が最も大きく39%であった。
各々、表2に示す粉末状PTFEを用い、その他は実施例1と同様にして、固体電解質層を作製した。
表2に示す粉末状PTFEをふるいにかけずに用いた他は、実施例1と同様にして、固体電解質層を作製した。
硫化物系固体電解質(0.75Li2S・0.25P2S5)と表2に示す粉末状PTFEとを秤量し、乳鉢にて200rpmで1時間撹拌し混合物を得た。
なお、粉末状のPTFEは真空乾燥機にて50℃、1時間乾燥して用いた。固形分は質量比で固体電解質:結着剤=95:5となるようにした。
得られた混合物をバルク状に成形し、シート状に圧延した。
その後、先程得られた圧延シートを2つに折りたたむことにより粗砕して、再度バルク状に成形した後、平らな板の上で金属ロールを用いてシート状に圧延することで、フィブリル化を促進させる工程を四度繰り返した。
その後、更に圧延することで、厚さ500μmのシート状固体電解質層を得た。さらに、シート状固体電解質層を切り出し、プレス機に投入し圧延をおこなった。さらに、8kNの荷重を繰り返しかけて厚みを調整した。最終的な固体電解質層の厚みは150μmになるようにギャップを調整した。なお、上記作業はArグローボックス内(露点約-80℃)で行った。初回の圧延率が最も大きく61%であった。
表2に示す粉末状PTFEを用い、その他は比較例1と同様にして、シート状固体電解質層を作製した。
VDF:HFPの共重合体をバインダー用意し、これを酪酸ブチル(キシダ化学社製)中に添加し、ミックスローターにて撹拌し、バインダー溶液を調製した。ここで、バインダー溶液全体を100質量%としてバインダーが5質量%含まれるようにした。結着剤溶液に、硫化物系固体電解質(0.75Li2S・0.25P2S5)を添加し、超音波ホモジナイザーを用いて超音波処理行うことで、硫化物系固体電解質とバインダーとが分散した「固体電解質層用スラリー」を得た。固形分は質量比で固体電解質:結着剤=95:5となるようにした。最終的に得られたスラリーにおいては、固形分比率が68質量%であった。作製した電解質スラリーを剥離可能な基材上にドクターブレードを用いて塗工し、乾燥させた。その後、プレスを行い、実施例1と同じ密度に成るよう、プレスを行い、固体電解質ペレットを作製した。なお、上記作業はArグローボックス内(露点約-80℃)で行った。
[含有水分量測定]
粉末状のPTFEは真空乾燥機にて50℃、1時間乾燥して用いた。真空乾燥後のPTFEの水分量は、ボートタイプ水分気化装置を有するカールフィッシャー水分計(ADP-511/MKC-510N 京都電子工業(株)製)を使用し、水分気化装置で210℃に加熱して、気化させた水分を測定した。キャリアガスとして、窒素ガスを流量200mL/minで流し、測定時間を30分とした。また、カールフィッシャー試薬としてケムアクアを使用した。サンプル量は1.5gとした。
(1)走査型電子顕微鏡(S-4800型 日立製作所製)を用いて、シート状固体電解質層の拡大写真(7000倍)を撮影し画像を得る。
(2)この画像に水平方向に等間隔で2本の線を引き、画像を三等分する。
(3)上方の直線上にある全てのPTFE繊維について、PTFE繊維1本あたり3箇所の直径を測定し、平均した値を当該PTFE繊維の直径とする。測定する3箇所は、PTFE繊維と直線との交点、交点からそれぞれ上下0.5μmずつずらした場所を選択する。(未繊維化のPTFE一次粒子は除く)。
(4)上記(3)の作業を、下方の直線上にある全てのPTFE繊維に対して行う。
(5)1枚目の画像を起点に画面右方向に1mm移動し、再度撮影を行い、上記(3)及び(4)によりPTFE繊維の直径を測定する。これを繰り返し、測定した繊維数が80本を超えた時点で終了とする。
(6)上記測定した全てのPTFE繊維の直径の中央値をフィブリル径の大きさとした。
導電率を以下の方法により測定した。
作製した固体電解質シートの表面にスパッタにより金電極を作製した後、Φ10mmに打ち抜いた。ステンレス集電体で挟み込んで測定用セルとした。このセルを乾燥アルゴン雰囲気中で、インピーダンスアナライザ(ソーラトロン社製1260型)を用いて、周波数範囲0.1Hz~8MHzで交流インピーダンス測定を行い、導電率を決定した。比較例1の値を100%として規格した。
作製した固体電解質シートを縦2cm、横6cmに切り取り試験片とした。直径4mmサイズの丸棒に巻き付けた後、目視で試験片を確認し、以下の基準で評価した。傷や割れが確認されない場合は○、ひび割れが確認された場合は×と評価した。
デジタルフォースゲージ(イマダ製 ZTS-20N)を使用して、100mm/分の条件下、4mm幅の短冊状の電極合剤試験片にて測定した。チャック間距離は30mmとした。破断するまで変位を与え、測定した結果の最大応力を各サンプルの強度とした。比較例1の値を100%として規格した。
Claims (12)
- 固体電解質及び結着剤を含有する全固体二次電池用合剤であって、
結着剤は、ポリテトラフルオロエチレン樹脂であり、
ポリテトラルオロエチレン樹脂は、フィブリル径(中央値)が70nm以下の繊維状構造を有することを特徴とする全固体二次電池用合剤。 - リチウムイオン全固体二次電池用である請求項1記載の全固体二次電池用合剤。
- 硫化物系全固体二次電池用である請求項1又は2記載の全固体二次電池用合剤。
- 固体電解質及び結着剤を含有する原料組成物を使用して得られた請求項1記載の全固体二次電池用合剤であって、
原料組成物は、結着剤が粉末状のポリテトラフルオロエチレン樹脂である請求項1記載の全固体二次電池用合剤。 - 原料組成物は、実質的に液体媒体を含有しない請求項4記載の全固体二次電池用合剤。
- 粉末状のポリテトラフルオロエチレン樹脂は、水分含有量が500ppm以下である請求項4又は5記載の全固体二次電池用合剤。
- 粉末状のポリテトラフルオロエチレン樹脂は、標準比重が2.12~2.18である請求項4,5又は6記載の全固体二次電池用合剤。
- 粉末状のポリテトラフルオロエチレン樹脂は、二次粒子径が500μm以上のポリテトラフルオロエチレン樹脂を50質量%以上含む請求項4,5,6又は7記載の全固体二次電池用合剤。
- 粉末状のポリテトラフルオロエチレン樹脂は、二次粒子径が500μm以上のポリテトラフルオロエチレン樹脂を80質量%以上含む請求項4,5,6又は7記載の全固体二次電池用合剤。
- 請求項1~9いずれか1項に記載の全固体電池用合剤を含む全固体二次電池用合剤シート。
- 固体電解質及び結着剤を含む原料組成物を混合しながら、剪断力を付与する工程(1)
前記工程(1)によって得られた全固体二次電池用合剤をバルク状に成形する工程(2)及び
前記工程(2)によって得られたバルク状の全固体二次電池用合剤をシート状に圧延する工程(3)
を有する全固体二次電池用シートの製造方法であって、結着剤は、粉末状のポリテトラフルオロエチレン樹脂であることを特徴とする全固体二次電池用シートの製造方法。 - 請求項10に記載の全固体二次電池用合剤シートを有する全固体二次電池。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202180057556.2A CN116057742A (zh) | 2020-09-01 | 2021-08-31 | 全固态二次电池用合剂、全固态二次电池用合剂片及其制造方法以及全固态二次电池 |
JP2022546326A JPWO2022050252A1 (ja) | 2020-09-01 | 2021-08-31 | |
KR1020237010807A KR20230058153A (ko) | 2020-09-01 | 2021-08-31 | 전고체 이차 전지용 합제, 전고체 이차 전지용 합제 시트 및 그 제조 방법 그리고 전고체 이차 전지 |
EP21864310.4A EP4210140A1 (en) | 2020-09-01 | 2021-08-31 | All-solid-state secondary cell mixture, all-solid-state secondary cell mixture sheet, method for manufacturing same, and all-solid-state secondary cell |
US18/176,184 US20230231182A1 (en) | 2020-09-01 | 2023-02-28 | All-solid-state secondary battery mixture, all-solid-state secondary battery mixture sheet and production method thereof, and all-solid-state secondary battery |
JP2024108659A JP2024128021A (ja) | 2020-09-01 | 2024-07-05 | 全固体二次電池用合剤シートの製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020-146853 | 2020-09-01 | ||
JP2020146853 | 2020-09-01 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/176,184 Continuation US20230231182A1 (en) | 2020-09-01 | 2023-02-28 | All-solid-state secondary battery mixture, all-solid-state secondary battery mixture sheet and production method thereof, and all-solid-state secondary battery |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022050252A1 true WO2022050252A1 (ja) | 2022-03-10 |
Family
ID=80490978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2021/031852 WO2022050252A1 (ja) | 2020-09-01 | 2021-08-31 | 全固体二次電池用合剤、全固体二次電池用合剤シート及びその製造方法並びに全固体二次電池 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230231182A1 (ja) |
EP (1) | EP4210140A1 (ja) |
JP (2) | JPWO2022050252A1 (ja) |
KR (1) | KR20230058153A (ja) |
CN (1) | CN116057742A (ja) |
TW (1) | TW202224237A (ja) |
WO (1) | WO2022050252A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023167298A1 (ja) * | 2022-03-02 | 2023-09-07 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに固体二次電池 |
WO2023167299A1 (ja) * | 2022-03-02 | 2023-09-07 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 |
WO2023230245A1 (en) * | 2022-05-27 | 2023-11-30 | Wildcat Discovery Technologies, Inc. | Composite polymer ceramic electrolyte |
WO2024034674A1 (ja) * | 2022-08-10 | 2024-02-15 | ダイキン工業株式会社 | 電気化学デバイス用バインダー用ポリテトラフルオロエチレン、電気化学デバイス用バインダー、電極合剤、電極、及び、二次電池 |
WO2024136601A1 (ko) * | 2022-12-23 | 2024-06-27 | 주식회사 엘지에너지솔루션 | 고체 전해질막 및 이를 포함하는 전고체 전지 |
WO2024176955A1 (ja) * | 2023-02-21 | 2024-08-29 | 三井化学株式会社 | 電極用バインダー、電極合材層、電極合材層形成材料、電極合材層の製造方法、電極およびリチウムイオン二次電池 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102023126389B3 (de) | 2023-08-18 | 2024-07-11 | GM Global Technology Operations LLC | Doppelschicht-elektrolyt |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011258333A (ja) * | 2010-06-07 | 2011-12-22 | Asahi Glass Co Ltd | 二次電池用電極コンポジットの製造方法、二次電池用電極および二次電池 |
WO2012063622A1 (ja) | 2010-11-10 | 2012-05-18 | ダイキン工業株式会社 | 電気二重層キャパシタ用電解液 |
WO2012086710A1 (ja) | 2010-12-21 | 2012-06-28 | ダイキン工業株式会社 | ポリテトラフルオロエチレン混合物 |
WO2015080291A1 (ja) | 2013-11-29 | 2015-06-04 | ダイキン工業株式会社 | 二軸延伸多孔質膜 |
WO2019154438A1 (zh) * | 2018-02-11 | 2019-08-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | 固态电解质及其制备方法与应用 |
WO2020036055A1 (ja) * | 2018-08-13 | 2020-02-20 | 富士フイルム株式会社 | 固体電解質組成物、固体電解質含有シート、全固体二次電池用電極シート及び全固体二次電池 |
JP2020509565A (ja) * | 2017-05-15 | 2020-03-26 | エルジー・ケム・リミテッド | 全固体電池用固体電解質膜の製造方法及び該方法によって製造された固体電解質膜 |
CN112421114A (zh) * | 2019-08-21 | 2021-02-26 | 南京博驰新能源股份有限公司 | 一种固态电解质膜的制备加工方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4016666A1 (en) | 2014-04-18 | 2022-06-22 | Tesla, Inc. | Dry energy storage device electrode and methods of making the same |
-
2021
- 2021-08-31 EP EP21864310.4A patent/EP4210140A1/en active Pending
- 2021-08-31 KR KR1020237010807A patent/KR20230058153A/ko unknown
- 2021-08-31 JP JP2022546326A patent/JPWO2022050252A1/ja active Pending
- 2021-08-31 CN CN202180057556.2A patent/CN116057742A/zh active Pending
- 2021-08-31 WO PCT/JP2021/031852 patent/WO2022050252A1/ja active Application Filing
- 2021-09-01 TW TW110132474A patent/TW202224237A/zh unknown
-
2023
- 2023-02-28 US US18/176,184 patent/US20230231182A1/en active Pending
-
2024
- 2024-07-05 JP JP2024108659A patent/JP2024128021A/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011258333A (ja) * | 2010-06-07 | 2011-12-22 | Asahi Glass Co Ltd | 二次電池用電極コンポジットの製造方法、二次電池用電極および二次電池 |
WO2012063622A1 (ja) | 2010-11-10 | 2012-05-18 | ダイキン工業株式会社 | 電気二重層キャパシタ用電解液 |
WO2012086710A1 (ja) | 2010-12-21 | 2012-06-28 | ダイキン工業株式会社 | ポリテトラフルオロエチレン混合物 |
WO2015080291A1 (ja) | 2013-11-29 | 2015-06-04 | ダイキン工業株式会社 | 二軸延伸多孔質膜 |
JP2020509565A (ja) * | 2017-05-15 | 2020-03-26 | エルジー・ケム・リミテッド | 全固体電池用固体電解質膜の製造方法及び該方法によって製造された固体電解質膜 |
WO2019154438A1 (zh) * | 2018-02-11 | 2019-08-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | 固态电解质及其制备方法与应用 |
WO2020036055A1 (ja) * | 2018-08-13 | 2020-02-20 | 富士フイルム株式会社 | 固体電解質組成物、固体電解質含有シート、全固体二次電池用電極シート及び全固体二次電池 |
CN112421114A (zh) * | 2019-08-21 | 2021-02-26 | 南京博驰新能源股份有限公司 | 一种固态电解质膜的制备加工方法 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023167298A1 (ja) * | 2022-03-02 | 2023-09-07 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに固体二次電池 |
WO2023167299A1 (ja) * | 2022-03-02 | 2023-09-07 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 |
JP2023129369A (ja) * | 2022-03-02 | 2023-09-14 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 |
JP7485998B2 (ja) | 2022-03-02 | 2024-05-17 | ダイキン工業株式会社 | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 |
WO2023230245A1 (en) * | 2022-05-27 | 2023-11-30 | Wildcat Discovery Technologies, Inc. | Composite polymer ceramic electrolyte |
WO2024034674A1 (ja) * | 2022-08-10 | 2024-02-15 | ダイキン工業株式会社 | 電気化学デバイス用バインダー用ポリテトラフルオロエチレン、電気化学デバイス用バインダー、電極合剤、電極、及び、二次電池 |
WO2024136601A1 (ko) * | 2022-12-23 | 2024-06-27 | 주식회사 엘지에너지솔루션 | 고체 전해질막 및 이를 포함하는 전고체 전지 |
WO2024176955A1 (ja) * | 2023-02-21 | 2024-08-29 | 三井化学株式会社 | 電極用バインダー、電極合材層、電極合材層形成材料、電極合材層の製造方法、電極およびリチウムイオン二次電池 |
Also Published As
Publication number | Publication date |
---|---|
KR20230058153A (ko) | 2023-05-02 |
CN116057742A (zh) | 2023-05-02 |
EP4210140A1 (en) | 2023-07-12 |
TW202224237A (zh) | 2022-06-16 |
JP2024128021A (ja) | 2024-09-20 |
JPWO2022050252A1 (ja) | 2022-03-10 |
US20230231182A1 (en) | 2023-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022138942A1 (ja) | 固体二次電池用シートの製造方法及び固体二次電池用結着剤 | |
WO2022050252A1 (ja) | 全固体二次電池用合剤、全固体二次電池用合剤シート及びその製造方法並びに全固体二次電池 | |
WO2022050251A1 (ja) | 二次電池用電極合剤、二次電池用電極合剤シート及びその製造方法並びに二次電池 | |
JP7350049B2 (ja) | 単層カーボンナノチューブとptfeとを複合した結着剤並びにそれを用いた電極作製用組成物及び二次電池 | |
JP7364973B2 (ja) | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 | |
WO2023167297A1 (ja) | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに固体二次電池 | |
JP7364972B2 (ja) | 二次電池用合剤、二次電池用合剤シート、二次電池用合剤シートの製造方法及び二次電池 | |
JP7486006B2 (ja) | 固体二次電池用シートの製造方法、固体二次電池電極用結着剤、電極作製用組成物、電極合剤、及び、電極 | |
JP7485999B2 (ja) | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 | |
JP7485998B2 (ja) | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに二次電池 | |
CN118786547A (en) | Mixture for secondary battery, mixture sheet for secondary battery, method for producing same, and secondary battery | |
CN118786545A (en) | Mixture for secondary battery, mixture sheet for secondary battery, method for producing same, and secondary battery | |
KR20240144327A (ko) | 이차 전지용 합제, 이차 전지용 합제 시트 및 그 제조 방법 그리고 이차 전지 | |
WO2023167298A1 (ja) | 二次電池用合剤、二次電池用合剤シート及びその製造方法並びに固体二次電池 | |
CN118805274A (en) | Mixture for secondary battery, mixture sheet for secondary battery, method for producing same, and secondary battery | |
CN118805273A (en) | Mixture for secondary battery, mixture sheet for secondary battery, method for producing same, and solid-state secondary battery | |
KR20240144328A (ko) | 이차 전지용 합제, 이차 전지용 합제 시트 및 그 제조 방법 그리고 고체 이차 전지 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21864310 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2022546326 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20237010807 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202337023057 Country of ref document: IN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2021864310 Country of ref document: EP Effective date: 20230403 |