JPWO2019135341A1 - 固体電解質材料、および、電池 - Google Patents
固体電解質材料、および、電池 Download PDFInfo
- Publication number
- JPWO2019135341A1 JPWO2019135341A1 JP2019563951A JP2019563951A JPWO2019135341A1 JP WO2019135341 A1 JPWO2019135341 A1 JP WO2019135341A1 JP 2019563951 A JP2019563951 A JP 2019563951A JP 2019563951 A JP2019563951 A JP 2019563951A JP WO2019135341 A1 JPWO2019135341 A1 JP WO2019135341A1
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- electrolyte material
- crystal phase
- range
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 203
- 239000000463 material Substances 0.000 title claims abstract description 153
- 239000013078 crystal Substances 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 230000002950 deficient Effects 0.000 claims abstract description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 68
- 238000002441 X-ray diffraction Methods 0.000 claims description 40
- 239000000460 chlorine Substances 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims 2
- 239000002245 particle Substances 0.000 description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 23
- 229910001416 lithium ion Inorganic materials 0.000 description 23
- 239000000843 powder Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- -1 etc.) Inorganic materials 0.000 description 15
- 229910003002 lithium salt Inorganic materials 0.000 description 15
- 159000000002 lithium salts Chemical class 0.000 description 15
- 238000003991 Rietveld refinement Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 13
- 230000007704 transition Effects 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003125 aqueous solvent Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000007812 deficiency Effects 0.000 description 6
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002001 electrolyte material Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910009523 YCl3 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013375 LiC Inorganic materials 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 2
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 2
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 229920001940 conductive polymer Chemical class 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910018127 Li 2 S-GeS 2 Inorganic materials 0.000 description 1
- 229910018133 Li 2 S-SiS 2 Inorganic materials 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910006020 NiCoAl Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 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
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/36—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 halogen being the only anion, e.g. NaYF4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/02—Amorphous compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- H01M2300/008—Halides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Conductive Materials (AREA)
Abstract
Description
Li3Y1Cl6・・・式(1)
実施の形態1における固体電解質材料は、第1結晶相を含む、固体電解質材料である。
Li3Y1Cl6・・・式(1)
Li3−3δY1+δCl6・・・式(2)
ここで、0<δ≦0.15、である。
実施の形態1における固体電解質材料は、例えば、下記の方法により、製造されうる。
以下、実施の形態2が説明される。上述の実施の形態1と重複する説明は、適宜、省略される。
[固体電解質材料の作製]
露点−60℃以下のアルゴン雰囲気で、原料粉LiClとYCl3とを、モル比でLiCl:YCl3=2.7:1.1となるように、秤量した。これらを乳鉢で粉砕して混合した。その後、遊星型ボールミルを用い、25時間、600rpmでミリング処理した。さらに、焼成炉で、Ar(アルゴン)雰囲気下、400℃で、48時間焼成処理を行った。
図3は、イオン伝導度の評価方法を示す模式図である。
図4は、固体電解質のイオン伝導度の温度依存性を示すグラフである。
図5は、XRDパターンを示すグラフである。
アルゴングローブボックス内で、実施例1の固体電解質材料と、活物質であるLiCoO2を、70:30の体積比率で秤量した。これらをメノウ乳鉢で混合することで、合剤を作製した。
図6は、初期放電特性を示すグラフである。
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=2.85:1.05のモル比で混合した。
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=2.91:1.03のモル比で混合した。
(xLi,Total/xY,Total)(1+δ)=xLiCl/xLYC+(3−3δ)・・・式(A1)
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=3:1のモル比で混合した。
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=3.3:0.9のモル比で混合した。
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=2.55:1.15のモル比で混合した。
(xY,Total/xLi,Total)(3−3δ)=xYCl3/xLYC+(1+δ)・・・式(A2)
固体電解質の原料粉として、LiClとYCl3とを用いて、LiCl:YCl3=2.25:1.25のモル比で混合した。
露点−30℃以下のドライ雰囲気で、原料粉LiBrとInBr3とを、モル比でLiBr:InBr3=3:1となるように、秤量した。これらを乳鉢で粉砕して混合した。その後、ペレット状に加圧成形した試料を、ガラス管中に真空封入を行い、200℃で1週間焼成を行った。
固体電解質の原料粉として、LiClとFeCl2とを用い、LiCl:FeCl2=2:1のモル比で混合した。これにより、比較例2の固体電解質材料であるLi2FeCl4を得た。
実施例1から7と比較例1、2とを比較すると、Li:Yモル比が3未満であるLi3−3δY1+δCl6の結晶相を含む固体電解質材料であれば、室温近傍において、5×10−5S/cm以上の高いイオン伝導性を示すことがわかる。また、−30℃から80℃の範囲において、相転移をしないことがわかる。すなわち、実施例1から7は、電池の想定動作温度域において、構造が安定であることがわかる。
201 正極
202 電解質層
203 負極
204 正極活物質粒子
205 負極活物質粒子
300 加圧成形用ダイス
301 枠型
302 パンチ下部
303 パンチ上部
1000 電池
Claims (13)
- 第1結晶相を含み、
前記第1結晶相の組成は、下記の組成式(1)により表される組成に比べて、Liが欠損している、
Li3Y1Cl6・・・式(1)
固体電解質材料。 - 前記第1結晶相は、下記の組成式(2)により表され、
Li3−3δY1+δCl6・・・式(2)
ここで、0<δ≦0.15、である、
請求項1に記載の固体電解質材料。 - 0.01≦δ≦0.133、である、
請求項2に記載の固体電解質材料。 - Cu−Kα線をX線源として用いることにより得られた、前記固体電解質材料のX線回折パターンは、回折角2θの値が30.34°以上32.36°以下である第1範囲内、前記回折角2θの値が39.51°以上42.07°以下である第2範囲内、及び前記回折角2θの値が47.18°以上50.30°以下である第3範囲内の各々において、ピークを含む、
請求項1から3のいずれかに記載の固体電解質材料。 - 前記X線回折パターンは、さらに、前記回折角2θの値が15.2°以上16.23°以下である第4範囲内、及び前記回折角2θの値が52.4°以上54.6°以下である第5範囲内の各々において、ピークを含む、
請求項4に記載の固体電解質材料。 - 前記X線回折パターンにおいて、前記第1範囲内に含まれる前記ピークの半値幅FWHMと、前記ピークの中心値2θpとが、
FWHM/2θp≦0.01、を満たす、
請求項4または5に記載の固体電解質材料。 - 前記第1結晶相は、塩素の副格子を含み、
前記副格子における塩素の配列は、六方最密充填構造が歪んだ原子配列を含む、
請求項1から6のいずれかに記載の固体電解質材料。 - 前記第1結晶相は、Li3YbCl6構造と同様の原子配列を含む、
請求項1から7のいずれかに記載の固体電解質材料。 - Cu−Kα線をX線源として用いることにより得られた、前記固体電解質材料のX線回折パターンは、回折角2θの値が29.18°以上31.03°以下である範囲内、及び前記回折角2θの値が33.83°以上36.00°以下である範囲内からなる群から選択される少なくとも1つにおいて、ピークを含む、
請求項1から8のいずれかに記載の固体電解質材料。 - 第2結晶相をさらに含み、
前記第2結晶相の母構造はLiClである、
請求項9に記載の固体電解質材料。 - Cu−Kα線をX線源として用いることにより得られた、前記固体電解質材料のX線回折パターンは、回折角2θの値が14.34°以上15.23°以下である範囲内、及び前記回折角2θの値が25.65°以上27.26°以下である範囲内からなる群から選択される少なくとも1つにおいて、ピークを含む、
請求項1から10のいずれかに記載の固体電解質材料。 - 第3結晶相をさらに含み、
前記第3結晶相の母構造はYCl3である、
請求項11に記載の固体電解質材料。 - 請求項1から12のいずれかに記載の固体電解質材料と、
正極と、
負極と、
前記正極と前記負極との間に設けられる電解質層と、
を備え、
前記正極、前記負極、及び前記電解質層からなる群から選択される少なくとも1つは、前記固体電解質材料を含む、
電池。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018000421 | 2018-01-05 | ||
JP2018000421 | 2018-01-05 | ||
PCT/JP2018/046256 WO2019135341A1 (ja) | 2018-01-05 | 2018-12-17 | 固体電解質材料、および、電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2019135341A1 true JPWO2019135341A1 (ja) | 2020-12-17 |
JP7165898B2 JP7165898B2 (ja) | 2022-11-07 |
Family
ID=67143651
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019563951A Active JP7165898B2 (ja) | 2018-01-05 | 2018-12-17 | 固体電解質材料、および、電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11485646B2 (ja) |
EP (1) | EP3736823A4 (ja) |
JP (1) | JP7165898B2 (ja) |
CN (1) | CN111316379B (ja) |
WO (1) | WO2019135341A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11522217B2 (en) | 2020-04-14 | 2022-12-06 | Saint-Gobain Ceramics & Plastics, Inc. | Electrolyte material and methods of forming |
EP4104235A4 (en) | 2020-04-14 | 2023-11-01 | Saint-Gobain Ceramics & Plastics Inc. | ION CONDUCTING MATERIAL, ELECTROLYTE COMPRISING THE ION CONDUCTING MATERIAL AND METHOD FOR SHAPING |
JP7395016B2 (ja) | 2020-04-23 | 2023-12-08 | サン-ゴバン セラミックス アンド プラスティクス,インコーポレイティド | イオン伝導性層およびその形成方法 |
JP7389277B2 (ja) | 2020-04-23 | 2023-11-29 | サン-ゴバン セラミックス アンド プラスティクス,インコーポレイティド | イオン伝導性層およびその形成方法 |
JP7357881B2 (ja) | 2020-07-02 | 2023-10-10 | 帝人株式会社 | 電気光学効果を有するポリカーボネート及びその製造方法、並びに該ポリカーボネートを用いた光制御素子 |
EP4104236A4 (en) * | 2020-08-07 | 2023-08-02 | Saint-Gobain Ceramics & Plastics Inc. | ELECTROLYTE MATERIAL AND METHOD OF MANUFACTURE |
US11848414B2 (en) | 2021-05-17 | 2023-12-19 | Saint-Gobain Ceramics & Plastics, Inc. | Electrolyte material and methods of forming |
US11942282B1 (en) * | 2021-07-13 | 2024-03-26 | National Technology & Engineering Solutions Of Sandia, Llc | Thermally sensitive state change ionic redox transistor |
CN117652040A (zh) * | 2021-07-19 | 2024-03-05 | 松下知识产权经营株式会社 | 正极材料和电池 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019135348A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 固体電解質材料、および、電池 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5108205B2 (ja) * | 2005-02-28 | 2012-12-26 | 国立大学法人静岡大学 | 全固体型リチウム二次電池 |
JP5141675B2 (ja) | 2009-12-16 | 2013-02-13 | トヨタ自動車株式会社 | 硫化物固体電解質材料の製造方法、硫化物固体電解質材料およびリチウム電池 |
JP5443445B2 (ja) * | 2011-07-06 | 2014-03-19 | トヨタ自動車株式会社 | 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
FR3004467B1 (fr) * | 2013-04-12 | 2016-05-27 | Saint-Gobain Cristaux Et Detecteurs | Fabrication d'une elpasolite stoechiometrique |
JP6003831B2 (ja) * | 2013-06-28 | 2016-10-05 | トヨタ自動車株式会社 | 硫化物固体電解質材料、硫化物ガラス、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
CN104953175A (zh) * | 2014-03-28 | 2015-09-30 | 比亚迪股份有限公司 | 一种锂离子电池固体电解质及其制备方法和锂离子电池 |
CN105254184A (zh) * | 2015-11-27 | 2016-01-20 | 宁波大学 | 一种稀土离子掺杂的Li3YCl6微晶玻璃及其制备方法 |
CN115036565A (zh) * | 2016-08-04 | 2022-09-09 | 松下知识产权经营株式会社 | 固体电解质材料和电池 |
-
2018
- 2018-12-17 EP EP18898263.1A patent/EP3736823A4/en active Pending
- 2018-12-17 WO PCT/JP2018/046256 patent/WO2019135341A1/ja unknown
- 2018-12-17 CN CN201880071191.7A patent/CN111316379B/zh active Active
- 2018-12-17 JP JP2019563951A patent/JP7165898B2/ja active Active
-
2020
- 2020-06-25 US US16/911,596 patent/US11485646B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019135348A1 (ja) * | 2018-01-05 | 2019-07-11 | パナソニックIpマネジメント株式会社 | 固体電解質材料、および、電池 |
Non-Patent Citations (1)
Title |
---|
BOHNSACK ANDREAS ET AL.: "Ternary Chlorides of the Rare-Earth Elements with Lithium, Li3MCl6(M=Tb-Lu, Y, Sc):Synthesis, Crysta", JOURNAL OF INORGANIC AND GENERAL CHEMISTRY, vol. Vol.623/Issue 7, JPN6022027809, July 1997 (1997-07-01), pages 1067 - 1073, ISSN: 0004818061 * |
Also Published As
Publication number | Publication date |
---|---|
JP7165898B2 (ja) | 2022-11-07 |
WO2019135341A1 (ja) | 2019-07-11 |
CN111316379B (zh) | 2022-04-26 |
CN111316379A (zh) | 2020-06-19 |
US20200328456A1 (en) | 2020-10-15 |
EP3736823A4 (en) | 2021-03-10 |
EP3736823A1 (en) | 2020-11-11 |
US11485646B2 (en) | 2022-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6934626B2 (ja) | 固体電解質材料、および、電池 | |
JP7253706B2 (ja) | 固体電解質材料、および、電池 | |
JP7253707B2 (ja) | 固体電解質材料、および、電池 | |
JP7417927B2 (ja) | 固体電解質材料、および、電池 | |
WO2019146218A1 (ja) | 固体電解質材料、および、電池 | |
WO2019135318A1 (ja) | 固体電解質材料、および、電池 | |
WO2019135348A1 (ja) | 固体電解質材料、および、電池 | |
WO2019135316A1 (ja) | 固体電解質材料、および、電池 | |
WO2019135317A1 (ja) | 固体電解質材料、および、電池 | |
WO2019135347A1 (ja) | 固体電解質材料、および、電池 | |
JP7165898B2 (ja) | 固体電解質材料、および、電池 | |
JP7417926B2 (ja) | 固体電解質材料、および、電池 | |
JPWO2019135321A1 (ja) | 固体電解質材料、および、電池 | |
JP7445868B2 (ja) | 固体電解質材料、およびそれを用いた電池 | |
JP7165899B2 (ja) | 固体電解質材料、および、電池 | |
WO2020194897A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
JP7442144B2 (ja) | 固体電解質材料およびそれを用いた電池 | |
JP7417952B2 (ja) | 固体電解質材料およびそれを用いた電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210730 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220705 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220829 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221004 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221012 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 7165898 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |