WO2022249760A1 - 固体電解質材料およびそれを用いた電池 - Google Patents
固体電解質材料およびそれを用いた電池 Download PDFInfo
- Publication number
- WO2022249760A1 WO2022249760A1 PCT/JP2022/016859 JP2022016859W WO2022249760A1 WO 2022249760 A1 WO2022249760 A1 WO 2022249760A1 JP 2022016859 W JP2022016859 W JP 2022016859W WO 2022249760 A1 WO2022249760 A1 WO 2022249760A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- electrolyte material
- material according
- examples
- negative electrode
- Prior art date
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 168
- 239000000463 material Substances 0.000 title claims abstract description 148
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 26
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 description 20
- 239000012071 phase Substances 0.000 description 19
- 239000007773 negative electrode material Substances 0.000 description 16
- -1 lithium oxide halide Chemical class 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 229910003002 lithium salt Inorganic materials 0.000 description 11
- 159000000002 lithium salts Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 241000509980 Lialis Species 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 6
- 239000003125 aqueous solvent Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002847 impedance measurement Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000011255 nonaqueous electrolyte Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910013131 LiN 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
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 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
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 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
- 229910052718 tin Inorganic materials 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 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
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910018111 Li 2 S-B 2 S 3 Inorganic materials 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
- 229910003528 Li(Ni,Co,Al)O2 Inorganic materials 0.000 description 1
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 1
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 1
- 229910005313 Li14ZnGe4O16 Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910012631 LiTi2 Inorganic materials 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 group 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 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
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000008021 deposition Effects 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000002593 electrical impedance tomography Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- 239000002861 polymer material Substances 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- 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
-
- 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
Definitions
- the present disclosure relates to solid electrolyte materials and batteries using the same.
- Patent Document 1 discloses LiAlI 4 as a raw material for a lithium oxide halide solid phase electrolyte.
- Non-Patent Document 1 discloses LiAlCl 4 produced by a mechanochemical method as a solid electrolyte.
- An object of the present disclosure is to provide a solid electrolyte material suitable for improving lithium ion conductivity.
- the solid electrolyte material of the present disclosure contains a crystalline phase containing Li, M, and X, where M is at least one selected from the group consisting of Al, Ga, and In, and X is is at least one selected from the group consisting of Cl, Br, and I, the crystal phase belongs to the space group P2 1 /c, and the X-ray diffraction pattern obtained by X-ray diffraction measurement of the solid electrolyte material shows , the full width at half maximum of the diffraction peak of the crystal phase assigned to the crystal plane of Miller index (202) is 0.27° or more and 0.50° or less.
- FIG. 1 is a cross-sectional view of a battery 1000 according to the second embodiment.
- 2 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Example 1.
- FIG. 3 is a schematic diagram of a pressure molding die 300 used for evaluating the ionic conductivity of solid electrolyte materials.
- 4 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 1.
- FIG. 5 is a graph showing the initial discharge characteristics of the battery according to Example 1.
- the solid electrolyte material according to the first embodiment contains a crystal phase containing Li, M, and X.
- M is at least one selected from the group consisting of Al, Ga and In.
- X is at least one selected from the group consisting of Cl, Br and I;
- the crystalline phase belongs to the space group P2 1 /c.
- the full width at half maximum of the diffraction peak of the crystal phase attributed to the crystal plane of Miller index (202) is 0.27° or more and 0.50° or less. is.
- a solid electrolyte material is a solid electrolyte material suitable for improving lithium ion conductivity.
- Solid electrolyte materials for example, have high lithium ion conductivity. Therefore, solid electrolyte materials can be used to obtain batteries with excellent charge-discharge characteristics.
- An example of such a battery is an all-solid secondary battery.
- an example of high lithium ion conductivity is, for example, 2.5 ⁇ 10 ⁇ 5 S/cm or more near room temperature.
- Room temperature is, for example, 25°C.
- the solid electrolyte material can have, for example, an ionic conductivity of 2.5 ⁇ 10 ⁇ 5 S/cm or higher.
- lithium ions can conduct not only inside the crystallites but also on the surface of the crystallites.
- the crystallite size of the crystal phase is sufficient. It is small and the specific surface area of the crystallite is large, resulting in high ionic conductivity.
- the solid electrolyte material may contain elements that are unavoidably mixed. Examples of such elements are hydrogen, nitrogen or oxygen. Such elements can be present in the raw powder of the solid electrolyte material or in the atmosphere for manufacturing or storing the solid electrolyte material. Elements that are unavoidably mixed in the solid electrolyte material are, for example, 1 mol % or less.
- the solid electrolyte material may consist essentially of Li, M, and X in order to increase the ionic conductivity of the solid electrolyte material.
- the solid electrolyte material consists essentially of Li, M, and X
- the solid electrolyte material may consist only of Li, M, and X in order to increase the ionic conductivity of the solid electrolyte material.
- the crystalline phase contained in the solid electrolyte material may have a LiAlCl4 structure.
- LiAlCl4 structure in the present disclosure means having an X-ray diffraction pattern similar to LiAlCl4 disclosed in ICSD (Inorganic Crystal Structure Database) Collection Code (1040).
- a similar X-ray diffraction pattern means that the diffraction angle, relative peak intensity, and maximum intensity peak of the diffraction pattern may vary from those of LiAlCl4 depending on the types of elements contained in the solid electrolyte material, but the spectral shape is LiAlCl4 . It means that it is similar to that of 4 .
- the crystal phase contained in the solid electrolyte material may be represented by the following compositional formula (1).
- the solid electrolyte material represented by the compositional formula (1) is suitable for improving ionic conductivity.
- the full width at half maximum of the diffraction peak of the crystal phase attributed to the crystal plane of Miller index (202) is It may be 0.36° or more and 0.45° or less.
- the shape of the solid electrolyte material is not limited. Examples of such shapes are acicular, spherical, or ellipsoidal.
- the solid electrolyte material may be particles.
- the solid electrolyte material may have the shape of pellets or plates.
- the solid electrolyte material When the shape of the solid electrolyte material is particulate (for example, spherical), the solid electrolyte material may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less, or a median diameter of 0.5 ⁇ m or more and 10 ⁇ m or less. diameter. This allows good dispersion of the solid electrolyte material and other materials.
- median particle size is meant the particle size (d50) for which the cumulative deposition in the volume-based particle size distribution is equal to 50%.
- the volume-based particle size distribution is measured by, for example, a laser diffraction measurement device or an image analysis device.
- a solid electrolyte material is manufactured, for example, by the following method.
- two or more iodide raw powders are mixed so as to have the desired composition.
- the raw material powders may be mixed in pre-adjusted molar ratios to compensate for possible compositional changes in the synthesis process.
- Li metal, Al metal, and I 2 may be used as raw materials.
- a mixture of raw material powders is mechanochemically reacted with each other in a mixing device such as a planetary ball mill to obtain a reactant. That is, the raw material powders are reacted with each other using the method of mechanochemical milling.
- the reactants may be fired in vacuum or in an inert atmosphere.
- a mixture of raw material powders may be fired in vacuum or in an inert atmosphere to obtain a reactant.
- inert atmospheres include helium atmosphere, argon atmosphere, and nitrogen atmosphere.
- a solid electrolyte material can be obtained by these methods.
- a battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
- An electrolyte layer is disposed between the positive and negative electrodes.
- At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.
- the battery according to the second embodiment contains the solid electrolyte material according to the first embodiment, it has excellent charge/discharge characteristics.
- FIG. 1 is a cross-sectional view of a battery 1000 according to the second embodiment.
- a battery 1000 includes a positive electrode 201 , an electrolyte layer 202 and a negative electrode 203 .
- Electrolyte layer 202 is provided between positive electrode 201 and negative electrode 203 .
- a positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 100 .
- the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 100 .
- the solid electrolyte 100 is particles containing the solid electrolyte material according to the first embodiment.
- the solid electrolyte 100 may be particles containing the solid electrolyte material according to the first embodiment as a main component.
- a particle containing the solid electrolyte material according to the first embodiment as a main component means a particle in which the component contained in the largest molar ratio is the solid electrolyte material according to the first embodiment.
- the solid electrolyte 100 may be particles made of the solid electrolyte material according to the first embodiment.
- the positive electrode 201 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
- the material is, for example, the positive electrode active material 204 .
- cathode active materials 204 include lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides. is.
- lithium-containing transition metal oxides are Li(Ni,Co,Mn) O2 , Li(Ni,Co,Al) O2 or LiCoO2 .
- (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
- the shape of the positive electrode active material 204 is not limited to a specific shape.
- the cathode active material 204 may be particles.
- the positive electrode active material 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
- positive electrode active material 204 and solid electrolyte 100 can be well dispersed in positive electrode 201 . Thereby, the charge/discharge characteristics of the battery 1000 are improved.
- the positive electrode active material 204 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the positive electrode active material 204 is improved. This allows battery 1000 to operate at high output.
- the positive electrode active material 204 may have a larger median diameter than the solid electrolyte 100 . Thereby, the positive electrode active material 204 and the solid electrolyte 100 can be well dispersed in the positive electrode 201 .
- the ratio of the volume of the positive electrode active material 204 to the total volume of the positive electrode active material 204 and the volume of the solid electrolyte 100 is 0.30 or more and 0.95 or less.
- the positive electrode 201 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
- the electrolyte layer 202 contains an electrolyte material.
- the electrolyte material is, for example, a solid electrolyte material.
- the electrolyte layer 202 may be a solid electrolyte layer.
- the electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 50% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 70% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may contain 90% by mass or more of the solid electrolyte material according to the first embodiment.
- the electrolyte layer 202 may consist only of the solid electrolyte material according to the first embodiment.
- the solid electrolyte material according to the first embodiment will be referred to as the first solid electrolyte material.
- a solid electrolyte material different from the first solid electrolyte material is referred to as a second solid electrolyte material.
- the electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material. In the electrolyte layer 202, the first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed. A layer made of the first solid electrolyte material and a layer made of the second solid electrolyte material may be stacked along the stacking direction of battery 1000 .
- the electrolyte layer 202 may consist only of the second solid electrolyte material.
- the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less. When the electrolyte layer 202 has a thickness of 1 ⁇ m or more, the short circuit between the positive electrode 201 and the negative electrode 203 is less likely to occur. If the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high power.
- the negative electrode 203 contains a material capable of intercalating and deintercalating metal ions such as lithium ions.
- the material is, for example, the negative electrode active material 205 .
- Examples of the negative electrode active material 205 are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
- the metallic material may be a single metal or an alloy.
- Examples of metallic materials are lithium metal or lithium alloys.
- Examples of carbon materials are natural graphite, coke, ungraphitized carbon, carbon fibers, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of negative electrode active materials are silicon (ie, Si), tin (ie, Sn), silicon compounds, or tin compounds.
- the shape of the negative electrode active material 205 is not limited to a specific shape.
- the negative electrode active material 205 may be particles.
- the negative electrode active material 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
- negative electrode active material 205 and solid electrolyte 100 can be well dispersed in negative electrode 203 . Thereby, the charge/discharge characteristics of the battery 1000 are improved.
- the negative electrode active material 205 has a median diameter of 100 ⁇ m or less, the diffusion rate of lithium in the negative electrode active material 205 is improved. This allows battery 1000 to operate at high output.
- the negative electrode active material 205 may have a larger median diameter than the solid electrolyte 100 . Thereby, the negative electrode active material 205 and the solid electrolyte 100 can be well dispersed in the negative electrode 203 .
- the ratio of the volume of the negative electrode active material 205 to the total volume of the negative electrode active material 205 and the volume of the solid electrolyte 100 is 0.30 or more and 0.95 or less.
- the negative electrode 203 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
- At least one selected from the group consisting of positive electrode 201, electrolyte layer 202, and negative electrode 203 contains a second solid electrolyte material for the purpose of enhancing ion conductivity, chemical stability, and electrochemical stability. may be
- the second solid electrolyte material may be a halide solid electrolyte.
- halide solid electrolytes are Li 2 MgX' 4 , Li 2 FeX' 4 , LiAlX' 4 , Li(Ga,In)X' 4 or Li 3 (Al,Ga,In)X' 6 .
- X' is at least one selected from the group consisting of F, Cl, Br and I.
- halide solid electrolyte is the compound represented by LipMeqYrZ6 .
- Me is at least one element selected from the group consisting of metal elements other than Li and Y and metalloid elements.
- Z is at least one selected from the group consisting of F, Cl, Br and I;
- m' represents the valence of Me.
- Simetallic elements are B, Si, Ge, As, Sb, and Te.
- Metallic element means all elements contained in groups 1 to 12 of the periodic table (excluding hydrogen) and all elements contained in groups 13 to 16 of the periodic table (however, , B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
- Me is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb. At least one may be selected.
- the second solid electrolyte material may be a sulfide solid electrolyte.
- sulfide solid electrolytes are Li 2 SP 2 S 5 , Li 2 S-SiS 2 , Li 2 S-B 2 S 3 , Li 2 S-GeS 2 , Li 3.25 Ge 0.25 P 0.75 S 4 , or Li10GeP2S12 . _
- the second solid electrolyte material may be an oxide solid electrolyte.
- oxide solid electrolytes are (i) NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof , (ii) perovskite-type solid electrolytes such as (LaLi) TiO3 , ( iii ) Li14ZnGe4O16 , Li LISICON-type solid electrolytes such as 4 SiO 4 , LiGeO 4 or elemental substitutions thereof, (iv) garnet-type solid electrolytes such as Li 7 La 3 Zr 2 O 12 or elemental substitutions thereof, or (v) Li 3 PO 4 or its N-substitution.
- NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof
- perovskite-type solid electrolytes such as (LaLi) TiO3 , ( iii ) Li14ZnGe4O16 , Li LISICON-type solid electrolytes such as 4 SiO 4 , LiGeO
- the second solid electrolyte material may be an organic polymer solid electrolyte.
- organic polymer solid electrolytes are polymeric compounds and lithium salt compounds.
- the polymer compound may have an ethylene oxide structure. Since a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, the ionic conductivity can be further increased.
- lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )3 .
- One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 is composed of a non-aqueous electrolyte liquid, a gel electrolyte, or an ion electrolyte for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery. It may contain liquids.
- the non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
- non-aqueous solvents examples include cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
- cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
- linear carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
- examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
- linear ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
- An example of a cyclic ester solvent is ⁇ -butyrolactone.
- An example of a linear ester solvent is methyl acetate.
- fluorosolvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
- One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.
- lithium salts are LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN( SO2C2F5 ) 2 , LiN( SO2CF3 ) . ( SO2C4F9 ) , or LiC ( SO2CF3 )3 .
- One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.
- the lithium salt concentration is, for example, 0.5 mol/liter or more and 2 mol/liter or less.
- a polymer material impregnated with a non-aqueous electrolyte can be used as the gel electrolyte.
- examples of polymeric materials are polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or polymers with ethylene oxide linkages.
- ionic liquids examples include (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium, (ii) pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums , piperaziniums, or aliphatic cyclic ammoniums such as piperidiniums, or (iii) nitrogen-containing heterocyclic aromatic cations such as pyridiniums or imidazoliums.
- aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium
- pyrrolidiniums morpholiniums, imidazoliniums, tetrahydropyrimidiniums , piperaziniums, or aliphatic cyclic ammoniums such as piperidiniums
- nitrogen-containing heterocyclic aromatic cations such as pyri
- Examples of anions contained in the ionic liquid are PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ , AsF 6 ⁇ , SO 3 CF 3 ⁇ , N(SO 2 CF 3 ) 2 ⁇ , N(SO 2 C 2 F 5 ) 2- , N ( SO2CF3 ) ( SO2C4F9 )- , or C ( SO2CF3 ) 3- .
- the ionic liquid may contain a lithium salt.
- At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder for the purpose of improving adhesion between particles.
- binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, Polyacrylic acid hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene-butadiene rubber , or carboxymethyl cellulose.
- Copolymers can also be used as binders.
- binders are tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid , and hexadiene.
- a mixture of two or more selected from the above materials may be used as the binder.
- At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include (i) graphites such as natural or artificial graphite, (ii) carbon blacks such as acetylene black or ketjen black, (iii) conductive materials such as carbon fibers or metal fibers. (iv) carbon fluoride, (v) metal powders such as aluminum, (vi) conductive whiskers such as zinc oxide or potassium titanate, (vii) conductive metal oxides such as titanium oxide. or (viii) a conductive polymeric compound such as polyaniline, polypyrrole, or polythiophene. For cost reduction, the conductive aid (i) or (ii) may be used.
- Examples of the shape of the battery according to the second embodiment are coin-shaped, cylindrical, rectangular, sheet-shaped, button-shaped, flat-shaped, and laminated.
- Example 1 Preparation of solid electrolyte material
- These raw powders were ground and mixed in a mortar. Thus, a mixed powder was obtained.
- the mixed powder was milled at 500 revolutions per minute (rpm) for 100 hours using a planetary ball mill.
- a zirconia pot with a capacity of 45 mL and 50 g of zirconia balls with a diameter of 5 mm were used in the milling process.
- the solid electrolyte material powder according to Example 1 was obtained.
- the Li content per unit weight of the solid electrolyte material according to Example 1 was measured by atomic absorption spectrometry.
- the Al content and I content of the solid electrolyte material according to Example 1 were measured by high frequency inductively coupled plasma atomic emission spectrometry. Based on the contents of Li, Al, and I obtained from these measurement results, the molar ratio of Li:Al:I was calculated.
- (X-ray diffraction measurement) 2 is a graph showing an X-ray diffraction pattern of the solid electrolyte material according to Example 1.
- FIG. 2 the vertical axis indicates the X-ray diffraction intensity, and the horizontal axis indicates the diffraction angle 2 ⁇ .
- the results shown in Figure 2 were measured by the following method.
- the solid electrolyte material according to Example 1 was sampled in an airtight jig for X-ray diffraction measurement in an argon atmosphere glove box having a dew point of -60°C or less.
- the X-ray diffraction pattern of the solid electrolyte material according to Example 1 was measured in a dry atmosphere having a dew point of ⁇ 45° C. or less using an X-ray diffraction device (MiniFlex 600, manufactured by RIGAKU).
- Cu-K ⁇ rays (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) were used as the X-ray source.
- FIG. 3 is a schematic diagram showing a pressure molding die 300 used to evaluate the ionic conductivity of solid electrolyte materials.
- the pressure forming die 300 had a punch upper part 301 , a frame mold 302 and a punch lower part 303 . Both the punch upper portion 301 and the punch lower portion 303 were made of electronically conductive stainless steel.
- the frame mold 302 was made of insulating polycarbonate.
- the ionic conductivity of the solid electrolyte material according to Example 1 was measured by the following method.
- the solid electrolyte material powder according to Example 1 (that is, the solid electrolyte material powder 101 in FIG. 3) was filled inside the pressure molding die 300 . Inside the pressing die 300, a pressure of 300 MPa was applied to the solid electrolyte material powder 101 according to Example 1 using an upper punch 301 and a lower punch 303. As shown in FIG.
- the upper punch 301 and lower punch 303 were connected to a potentiostat (Princeton Applied Research, VersaSTAT4) equipped with a frequency response analyzer.
- the punch upper part 301 was connected to the working electrode and the terminal for potential measurement.
- the punch bottom 303 was connected to the counter and reference electrodes.
- the impedance of the solid electrolyte material was measured by electrochemical impedance measurement at room temperature.
- FIG. 4 is a graph showing a Cole-Cole plot obtained by impedance measurement of the solid electrolyte material according to Example 1.
- FIG. 4 the vertical axis indicates the imaginary component of impedance, and the horizontal axis indicates the real component of impedance.
- the real value of the impedance at the measurement point where the absolute value of the phase of the complex impedance was the smallest was regarded as the resistance to ion conduction of the solid electrolyte material. See the arrow R se shown in FIG. 4 for the real value.
- the ionic conductivity was calculated based on the following formula (2) using the resistance value.
- ⁇ represents ionic conductivity.
- S represents the contact area of the solid electrolyte material with the punch upper part 301 .
- S represents the cross-sectional area of the hollow portion of the frame mold 302 in FIG.
- R se represents the resistance value of the solid electrolyte material in impedance measurement.
- t represents the thickness of the solid electrolyte material.
- t represents the thickness of the layer formed from the solid electrolyte material powder 101 in FIG.
- Li 6 PS 5 Cl 80 mg
- an algyrodite-type sulfide solid electrolyte 20 mg
- the above mixture 18 mg
- VGCF VGCF
- a metal In foil, a metal Li foil, and a metal In foil were laminated in this order on the solid electrolyte layer.
- a pressure of 40 MPa was applied to this laminate to form a second electrode.
- current collectors made of stainless steel were attached to the first electrode and the second electrode, and current collecting leads were attached to the current collectors.
- Example 1 a battery according to Example 1 was obtained.
- (Charging and discharging test) 5 is a graph showing the initial discharge characteristics of the battery according to Example 1.
- the battery according to Example 1 was placed in a constant temperature bath at 85°C.
- a cell according to Example 1 was charged at a current density of 67 ⁇ A/cm 2 until a voltage of 0.60 V was reached. This current density corresponds to a 0.05C rate.
- Example 1 The cell according to Example 1 was then discharged at a current density of 67 ⁇ A/cm 2 until a voltage of 1.05 V was reached.
- the battery according to Example 1 had an initial discharge capacity of 741 ⁇ Ah.
- Example 2 to 4 (Preparation of solid electrolyte material)
- Solid electrolyte materials according to Examples 2 to 4 were obtained in the same manner as in Example 1 except for the milling conditions.
- the milling conditions ie, ball size, rotation speed, and time.
- Batteries according to Examples 2 to 4 were obtained in the same manner as in Example 1, using the solid electrolyte materials according to Examples 2 to 4.
- the batteries according to Examples 2 to 4 like the battery according to Example 1, charged and discharged well.
- LiAlI 4 , LiAlCl 4 , LiGaI 4 , and LiInI 4 were prepared under the milling conditions shown in Table 1 as solid electrolyte materials according to Comparative Examples 1 to 8.
- the solid electrolyte materials according to Examples 1 to 4 and Comparative Examples 1 to 8 had crystal phases belonging to the space group P2 1 /c.
- lithium ions conduct not only inside the crystallites but also on the surface of the crystallites.
- the solid electrolyte material containing Ga or In in which M is a homologous element to Al belongs to the same space group P2 1 /c as LiAlI 4 which is the solid electrolyte material according to Example 1 and the like. Can form structures. Therefore, in the solid electrolyte in which M is Ga or In in the composition formula (1), if the full width at half maximum is adjusted in the same manner as in each example, the same effect as when M is Al can be expected.
- the solid electrolyte material containing Cl or Br in which X is a homologous element to I belongs to the same space group P2 1 /c as LiAlI 4 which is the solid electrolyte material according to Example 1 and the like. Can form structures. Therefore, a solid electrolyte in which X is Cl or Br in composition formula (1) can be expected to have the same effect as when X is I if the full width at half maximum is adjusted in the same manner as in each example.
- the solid electrolyte material according to the present disclosure is a material that can improve lithium ion conductivity, and is suitable for providing batteries that can be charged and discharged satisfactorily.
- the solid electrolyte material of the present disclosure is used, for example, in batteries such as all-solid lithium ion secondary batteries.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
Description
第1実施形態による固体電解質材料は、Li、M、およびXを含む結晶相を含有する。Mは、Al、Ga、およびInからなる群より選択される少なくとも1つである。Xは、Cl、Br、およびIからなる群より選択される少なくとも1つである。結晶相は、空間群P21/cに属している。固体電解質材料のX線回折測定によって得られるX線回折パターンにおいて、ミラー指数(202)の結晶面に帰属される結晶相の回折ピークの半値全幅が、0.27°以上かつ0.50°以下である。
固体電解質材料は、例えば、下記の方法により、製造される。
以下、第2実施形態が説明される。第1実施形態において説明された事項は、適宜、省略され得る。
(i)LiTi2(PO4)3またはその元素置換体のようなNASICON型固体電解質、(ii)(LaLi)TiO3のようなペロブスカイト型固体電解質、(iii)Li14ZnGe4O16、Li4SiO4、LiGeO4またはその元素置換体のようなLISICON型固体電解質、(iv)Li7La3Zr2O12またはその元素置換体のようなガーネット型固体電解質、または(v)Li3PO4またはそのN置換体、である。
(固体電解質材料の作製)
-60℃以下の露点を有するアルゴン雰囲気(以下、「乾燥アルゴン雰囲気」という)中で、原料粉としてLiIおよびAlI3が、LiI:AlI3=1:1のモル比となるように用意された。これらの原料粉が乳鉢中で粉砕され、混合された。このようにして、混合粉が得られた。混合粉は、遊星型ボールミルを用い、100時間、500回転/分(rpm)でミリング処理された。ミリング処理において、容量45mLのジルコニアポットと直径5mmのジルコニアボール50gが使用された。このようにして、実施例1による固体電解質材料の粉末が得られた。
図2は、実施例1による固体電解質材料のX線回折パターンを示すグラフである。図2において、縦軸はX線回折強度を示し、横軸は回折角2θを示す。図2に示される結果は、下記の方法により測定された。
図3は、固体電解質材料のイオン伝導度を評価するために用いられた加圧成形ダイス300を示す模式図である。
乾燥アルゴン雰囲気中で、実施例1による固体電解質材料、Li4Ti5O12、およびカーボンファイバー(VGCF)が、65:30:5の重量比となるように用意された。これらの材料は、乳鉢中で混合された。このようにして、混合物が得られた。なお、「VGCF」は、昭和電工株式会社の登録商標である。
図5は、実施例1による電池の初期放電特性を示すグラフである。図5において、縦軸は電圧を示し、横軸は容量を示す。初期放電特性は、下記の方法により、測定された。
(固体電解質材料の作製)
実施例2から4では、原料粉として、LiIおよびAlI3が、LiI:AlI3=1:1のモル比となるように用意された。
実施例2から4による固体電解質材料のイオン伝導度が、実施例1と同様に測定された。測定結果は、表1に示される。
実施例2から4による固体電解質材料が用いられ、実施例1と同様にして、実施例2から4による電池が得られた。実施例2から4による電池は、実施例1による電池と同様に、良好に充電および放電された。
(固体電解質材料の作製)
比較例1から8による固体電解質材料として、LiAlI4、LiAlCl4、LiGaI4、およびLiInI4、が表1に示されるミリング処理の条件によって用意された。
比較例1から8による固体電解質材料のイオン伝導度は、実施例1と同様に測定された。測定結果は、表1に示される。
表1から明らかなように、実施例1から4による固体電解質材料は、室温近傍において、2.5×10-5S/cm以上の高いイオン伝導度を有していた。
101 固体電解質材料の粉末
201 正極
202 電解質層
203 負極
204 正極活物質
205 負極活物質
300 加圧成形ダイス
301 パンチ上部
302 枠型
303 パンチ下部
1000 電池
Claims (8)
- 固体電解質材料であって、
Li、M、およびXを含む結晶相を含有し、
ここで、Mは、Al、Ga、およびInからなる群より選択される少なくとも1つであり、
Xは、Cl、Br、およびIからなる群より選択される少なくとも1つであり、
前記結晶相は、空間群P21/cに属し、
前記固体電解質材料のX線回折測定によって得られるX線回折パターンにおいて、ミラー指数(202)の結晶面に帰属される前記結晶相の回折ピークの半値全幅が、0.27°以上かつ0.50°以下である、
固体電解質材料。 - 前記結晶相は、LiAlCl4構造を有する、
請求項1に記載の固体電解質材料。 - 前記結晶相は、以下の組成式(1)により表され、
Li1-aMaX1+2a ・・・(1)
ここで、0<a<1、が充足される、
請求項1または2に記載の固体電解質材料。 - 前記組成式(1)において、0.01≦a≦0.50、が充足される、
請求項3に記載の固体電解質材料。 - 前記組成式(1)において、0.33≦a≦0.50、が充足される、
請求項4に記載の固体電解質材料。 - 前記組成式(1)において、a=0.50、が充足される、
請求項4または5に記載の固体電解質材料。 - 前記半値全幅は、0.36°以上かつ0.45°以下である、
請求項1から6のいずれか一項に記載の固体電解質材料。 - 正極、
負極、および
前記正極および前記負極の間に設けられている電解質層、
を備え、
前記正極、前記負極、および前記電解質層からなる群より選択される少なくとも1つは、請求項1から7のいずれか一項に記載の固体電解質材料を含有する、
電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023523333A JPWO2022249760A1 (ja) | 2021-05-27 | 2022-03-31 | |
CN202280034722.1A CN117296108A (zh) | 2021-05-27 | 2022-03-31 | 固体电解质材料及使用该固体电解质材料的电池 |
US18/503,463 US20240072301A1 (en) | 2021-05-27 | 2023-11-07 | Solid electrolyte material and battery using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021089635 | 2021-05-27 | ||
JP2021-089635 | 2021-05-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/503,463 Continuation US20240072301A1 (en) | 2021-05-27 | 2023-11-07 | Solid electrolyte material and battery using the same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022249760A1 true WO2022249760A1 (ja) | 2022-12-01 |
Family
ID=84228713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/016859 WO2022249760A1 (ja) | 2021-05-27 | 2022-03-31 | 固体電解質材料およびそれを用いた電池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240072301A1 (ja) |
JP (1) | JPWO2022249760A1 (ja) |
CN (1) | CN117296108A (ja) |
WO (1) | WO2022249760A1 (ja) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57103270A (en) * | 1980-10-24 | 1982-06-26 | Reiioo Baku Corp | Lithium oxide halide solid electrolyte |
-
2022
- 2022-03-31 CN CN202280034722.1A patent/CN117296108A/zh active Pending
- 2022-03-31 WO PCT/JP2022/016859 patent/WO2022249760A1/ja active Application Filing
- 2022-03-31 JP JP2023523333A patent/JPWO2022249760A1/ja active Pending
-
2023
- 2023-11-07 US US18/503,463 patent/US20240072301A1/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57103270A (en) * | 1980-10-24 | 1982-06-26 | Reiioo Baku Corp | Lithium oxide halide solid electrolyte |
Non-Patent Citations (1)
Title |
---|
FLORES-GONZÁLEZ NICOLÁS, MINAFRA NICOLÒ, DEWALD GEORG, REARDON HAZEL, SMITH RONALD I., ADAMS STEFAN, ZEIER WOLFGANG G., GREGORY DU: "Mechanochemical Synthesis and Structure of Lithium Tetrahaloaluminates, LiAlX 4 (X = Cl, Br, I): A Family of Li-Ion Conducting Ternary Halides", ACS MATERIALS LETTERS, vol. 3, no. 5, 3 May 2021 (2021-05-03), pages 652 - 657, XP093008783, ISSN: 2639-4979, DOI: 10.1021/acsmaterialslett.1c00055 * |
Also Published As
Publication number | Publication date |
---|---|
CN117296108A (zh) | 2023-12-26 |
US20240072301A1 (en) | 2024-02-29 |
JPWO2022249760A1 (ja) | 2022-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7316571B2 (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 | |
JP7417925B2 (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 | |
JP7418014B2 (ja) | 固体電解質材料およびそれを用いた電池 | |
JP7445868B2 (ja) | 固体電解質材料、およびそれを用いた電池 | |
JP7445876B2 (ja) | 固体電解質材料およびそれを用いた電池 | |
JP7445874B2 (ja) | 固体電解質材料、およびそれを用いた電池 | |
JP7417953B2 (ja) | 固体電解質およびそれを用いた電池 | |
JP7496509B2 (ja) | 固体電解質材料およびこれを用いた電池 | |
JP7417951B2 (ja) | リチウムイオン伝導性固体電解質材料、およびこれを用いた電池 | |
WO2023013232A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2023013305A1 (ja) | 正極材料、それを用いた電池、および電池の充電方法 | |
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 | |
JP7329776B2 (ja) | 固体電解質材料、およびこれを用いた電池 | |
WO2022249760A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2022249762A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2022264659A1 (ja) | 固体電解質材料および電池 | |
WO2022259749A1 (ja) | 固体電解質材料および電池 | |
WO2022249759A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2023013206A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2022254956A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2022254955A1 (ja) | 固体電解質材料およびそれを用いた電池 | |
WO2023181536A1 (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 |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22811034 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023523333 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280034722.1 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22811034 Country of ref document: EP Kind code of ref document: A1 |