WO2022254796A1 - 電極材料および電池 - Google Patents
電極材料および電池 Download PDFInfo
- Publication number
- WO2022254796A1 WO2022254796A1 PCT/JP2022/004783 JP2022004783W WO2022254796A1 WO 2022254796 A1 WO2022254796 A1 WO 2022254796A1 JP 2022004783 W JP2022004783 W JP 2022004783W WO 2022254796 A1 WO2022254796 A1 WO 2022254796A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- electrode
- solid electrolyte
- battery
- electrode material
- Prior art date
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 202
- 239000011149 active material Substances 0.000 claims abstract description 191
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 5
- 229910052752 metalloid Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 37
- 239000007774 positive electrode material Substances 0.000 description 29
- 239000007773 negative electrode material Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 20
- -1 Group 3 elements Inorganic materials 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002203 sulfidic glass Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910013184 LiBO Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 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
- 229910052795 boron group element Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910052800 carbon group element Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 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
- 239000007789 gas Substances 0.000 description 2
- 229910001849 group 12 element Inorganic materials 0.000 description 2
- 229910021480 group 4 element Inorganic materials 0.000 description 2
- 229910021478 group 5 element Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 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
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-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
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000002227 LISICON Substances 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910011229 Li7Ti5O12 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- 229910013392 LiN(SO2CF3)(SO2C4F9) Inorganic materials 0.000 description 1
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910012616 LiTi2O4 Inorganic materials 0.000 description 1
- 229910008291 Li—B—O Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 239000002033 PVDF binder Substances 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910009523 YCl3 Inorganic materials 0.000 description 1
- 229910021601 Yttrium(III) bromide Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 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
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium 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
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 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
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229940070721 polyacrylate Drugs 0.000 description 1
- 229920002239 polyacrylonitrile 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
- 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
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 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
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M10/056—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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- 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
- This disclosure relates to electrode materials and batteries.
- Patent Document 1 discloses a negative electrode material containing lithium titanate as a negative electrode active material and a solid electrolyte formed of a halide, and a battery using the same.
- the electrode material in one aspect of the present disclosure is a first active material containing Li, Ti, and O; a second active material containing Mo and O; a solid electrolyte; including.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an electrode material according to Embodiment 1.
- FIG. FIG. 2 is a cross-sectional view showing a schematic configuration of a battery according to Embodiment 2.
- FIG. 3 is a graph showing the results of an initial charge/discharge test of the battery in Example 4.
- Patent Document 1 discloses a battery using a negative electrode material containing lithium titanate as a negative electrode active material. Batteries using lithium titanate are known to exhibit high charge-discharge efficiency. In addition, lithium titanate is less likely to cause precipitation of lithium metal. Therefore, when lithium titanate is used for the negative electrode, it is possible to prevent an internal short circuit caused by the deposited metal penetrating the electrolyte layer and coming into contact with the positive electrode. Furthermore, lithium titanate is characterized by small expansion and contraction associated with insertion and extraction of lithium ions. Therefore, the use of lithium titanate as the active material can improve the safety of the battery. On the other hand, lithium titanate has a problem of small capacity per mass.
- the inventors diligently researched a technique for achieving both charge/discharge efficiency and discharge capacity. As a result, the inventors have arrived at the technique of the present disclosure.
- the electrode material according to the first aspect of the present disclosure is a first active material containing Li, Ti, and O; a second active material containing Mo and O; a solid electrolyte; including.
- the first active material containing Li, Ti, and O improves the charge/discharge efficiency of the battery.
- a second active material containing Mo and O improves the discharge capacity of the battery. Therefore, according to the above configuration, both the charge/discharge efficiency and the discharge capacity can be achieved.
- the ratio of the mass of the first active material to the total mass of the first active material and the second active material is 50% or more and It may be 99% or less.
- the first active material undergoes less expansion and contraction due to insertion and extraction of lithium ions than the second active material. Therefore, according to the above configuration, it is possible to improve the safety of the battery while achieving both the charge/discharge efficiency and the discharge capacity of the battery.
- the ratio may be 70% or more and 95% or less. According to the above configuration, it is possible to further improve the safety of the battery while achieving both the charge/discharge efficiency and the discharge capacity of the battery.
- the first active material may contain lithium titanium oxide. According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the lithium titanium oxide may contain Li4Ti5O12 . According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the second active material may contain molybdenum oxide. According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the molybdenum oxide may contain MoO2 . According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the solid electrolyte may contain Li, M, and X.
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements.
- X is at least one selected from the group consisting of F, Cl, Br and I; According to the above configuration, it is possible to improve the output characteristics of the battery.
- the solid electrolyte may be represented by the following compositional formula (1).
- ⁇ , ⁇ , and ⁇ are independently values greater than 0. According to the above configuration, it is possible to further improve the output characteristics of the battery.
- the solid electrolyte may contain Li3YBr2Cl2I2 . According to the above configuration, it is possible to further improve the output characteristics of the battery.
- the solid electrolyte may not contain sulfur. According to the above configuration, it is possible to improve the safety of the battery.
- the battery according to the twelfth aspect of the present disclosure includes a first electrode, a second electrode, and an electrolyte layer disposed between the first electrode and the second electrode; At least one selected from the group consisting of the first electrode and the second electrode includes the electrode material according to any one of the first to eleventh aspects.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an electrode material 1000 according to Embodiment 1.
- FIG. 1 is a cross-sectional view showing a schematic configuration of an electrode material 1000 according to Embodiment 1.
- the electrode material 1000 includes an active material 103 and a solid electrolyte 104.
- Active material 103 includes first active material 101 containing Li, Ti, and O, and second active material 102 containing Mo and O.
- FIG. 1 A diagrammatic representation of an active material 103 .
- the first active material 101 containing Li, Ti, and O improves the charge/discharge efficiency of the battery.
- the second active material 102 containing Mo and O improves the discharge capacity of the battery. Therefore, if the electrode material 1000 is used, both charge/discharge efficiency and discharge capacity can be achieved.
- the active material 103 may contain only the first active material 101 and the second active material 102 .
- “including only the first active material 101 and the second active material 102” means that the active material 103 is intentionally composed of materials other than the first active material 101 and the second active material 102, except for inevitable impurities. Means not added. For example, raw materials for the first active material 101 and the second active material 102, by-products generated when the first active material 101 and the second active material 102 are produced, and the like are included in the unavoidable impurities. The same applies to other substances.
- the mass ratio of the first active material 101 to the total mass of the first active material 101 and the second active material 102 may be 50% or more and 99% or less. Compared to the second active material 102, the first active material 101 expands and contracts less due to insertion and extraction of lithium ions. Therefore, according to the above configuration, it is possible to improve the safety of the battery while achieving both the charge/discharge efficiency and the discharge capacity of the battery.
- the ratio of the mass of the first active material 101 to the total mass of the first active material 101 and the second active material 102 can be calculated from the volumes of the first active material 101 and the second active material 102, for example. Specifically, by multiplying the volume of each of the first active material 101 and the second active material 102 by the density of each of the first active material 101 and the second active material 102, the first active material 101 and the second active material 102 can be calculated. From the calculated masses of first active material 101 and second active material 102, the ratio of the mass of first active material 101 to the total mass of first active material 101 and second active material 102 can be calculated.
- the volume of each of first active material 101 and second active material 102 can be measured, for example, from a cross-sectional SEM image obtained by a scanning electron microscope (SEM). Also, the density of each of the first active material 101 and the second active material 102 can be measured using, for example, a pycnometer.
- the mass ratio of the first active material 101 to the total mass of the first active material 101 and the second active material 102 may be 70% or more and 95% or less. According to the above configuration, it is possible to further improve the safety of the battery.
- the mass ratio of the first active material 101 to the total mass of the first active material 101 and the second active material 102 may be 75% or more and 80% or less. According to the above configuration, it is possible to further improve the safety of the battery.
- the first active material 101 may contain lithium titanium oxide. According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the first active material 101 may contain lithium titanium oxide as a main component.
- main component means a component contained at a mass ratio of 50% or more.
- the first active material 101 may contain 70% or more of lithium titanium oxide in mass ratio with respect to the entire first active material 101 .
- the first active material 101 may be lithium titanium oxide.
- Lithium titanium oxides include , for example , Li4Ti5O12 , Li7Ti5O12 , and LiTi2O4 .
- the lithium titanium oxide may contain at least one selected from these materials.
- the lithium titanium oxide may contain Li4Ti5O12 . According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the lithium titanium oxide may be Li4Ti5O12 .
- the second active material 102 may contain molybdenum oxide. According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the second active material 102 may contain molybdenum oxide as a main component.
- the second active material 102 may contain molybdenum oxide at a mass ratio of 70% or more with respect to the entire second active material 102 .
- the second active material 102 may be molybdenum oxide.
- Molybdenum oxides include MoO2 .
- Molybdenum oxide may include MoO2 . According to the above configuration, it is easier to achieve both the charge/discharge efficiency and the discharge capacity.
- the molybdenum oxide may be MoO2 .
- the solid electrolyte 104 may contain Li, M, and X.
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements.
- X is at least one selected from the group consisting of F, Cl, Br and I; According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be improved. Thereby, the output characteristics of the battery can be improved.
- metal elements are B, Si, Ge, As, Sb and Te.
- Metallic element means all elements contained in Groups 1 to 12 of the periodic table except hydrogen, and B, Si, Ge, As, Sb, Te, C, N, P, O, S, and All elements contained in groups 13 to 16 of the periodic table except Se. That is, the term “semimetallic element” or “metallic element” refers to a group of elements that can become cations when an inorganic compound is formed with a halogen element.
- the solid electrolyte 104 may consist essentially of Li, M, and X. “Consisting substantially of Li, M, and X” means that in the solid electrolyte 104, the molar ratio of the total amount of substances of Li, M, and X to the total amount of substances of all elements constituting the solid electrolyte 104 ( That is, it means that the molar fraction) is 90% or more. As an example, the molar ratio may be 95% or greater.
- the solid electrolyte 104 may consist of Li, M, and X only. "Consisting only of Li, M, and X” means that in the solid electrolyte 104, the molar ratio of the total amount of Li, M, and X to the total amount of all elements constituting the solid electrolyte 104 is 100%. means that
- the solid electrolyte 104 may be represented by the following compositional formula (1).
- composition formula (1) ⁇ , ⁇ , and ⁇ are each independently a value greater than 0. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved. Thereby, the output characteristics of the battery can be further improved.
- M is at least one selected from the group consisting of Group 1 elements, Group 2 elements, Group 3 elements, Group 4 elements, and lanthanoid elements. may contain. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- Group 1 elements include, for example, Na, K, Rb, and Cs.
- Group 2 elements include, for example, Mg, Ca, Sr, and Ba.
- Group 3 elements include Sc and Y, for example.
- Group 4 elements include, for example, Ti, Zr, and Hf.
- Lanthanide elements include, for example, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- solid electrolyte 104 contains Li, M, and X
- M contains at least one element selected from the group consisting of Group 5 elements, Group 12 elements, Group 13 elements, and Group 14 elements. good too. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- Group 5 elements include, for example, Nb and Ta.
- Examples of Group 12 elements include Zn.
- Group 13 elements include, for example, Al, Ga, and In.
- Examples of Group 14 elements include Sn.
- M is Na, K, Mg, Ca, Sr, Ba, Sc, Y, Zr, Hf, La, Ce, Pr, Nd, Sm, Eu, Gd. , Tb, Dy, Ho, Er, Tm, Yb, and Lu. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- M may contain at least one selected from the group consisting of Mg, Ca, Sr, Y, Sm, Gd, Dy, and Hf. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- X may contain at least one selected from the group consisting of Br, Cl, and I. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- the solid electrolyte 104 contains Li, M, and X
- X may contain Br, Cl, and I. According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved.
- the solid electrolyte 104 may be represented by the following compositional formula (2).
- X is at least one selected from the group consisting of F, Cl, Br and I.
- the solid electrolyte 104 may be represented by the following compositional formula (3).
- the solid electrolyte 104 may be represented by the following compositional formula (4).
- composition formula (4) 0 ⁇ x ⁇ 6 and 0 ⁇ y ⁇ 6 are satisfied.
- solid electrolyte 104 may be at least one selected from the group consisting of Li3YCl6 , Li3YBr6 , Li3YBr2Cl4 , and Li3YBr2Cl2I2 . good.
- the solid electrolyte 104 may contain Li3YBr2Cl2I2 . According to the above configuration, the ionic conductivity of the solid electrolyte 104 can be further improved. Thereby, the output characteristics of the battery can be further improved.
- the solid electrolyte 104 may contain Li3YBr2Cl2I2 as a main component.
- the solid electrolyte 104 may contain Li 3 YBr 2 Cl 2 I 2 at a mass ratio of 70% or more with respect to the solid electrolyte 104 as a whole.
- the solid electrolyte 104 may be Li3YBr2Cl2I2 .
- the solid electrolyte 104 may not contain sulfur. According to the above configuration, generation of hydrogen sulfide gas can be suppressed. Thereby, the safety of the battery can be improved.
- the shape of the solid electrolyte 104 is not limited.
- the shape of the solid electrolyte 104 may be, for example, acicular, spherical, oval, fibrous, or the like.
- the shape of the solid electrolyte 104 may be, for example, particulate.
- Solid electrolyte 104 may be formed to have a pellet shape or plate shape.
- the median diameter of the solid electrolyte 104 may be 0.1 ⁇ m or more and 100 ⁇ m or less. According to the above configuration, the active material 103 and the solid electrolyte 104 can form a good dispersion state in the electrode. This improves the charge/discharge characteristics of the battery.
- volume diameter means the particle size when the cumulative volume 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.
- the median diameter of the solid electrolyte 104 may be 0.5 ⁇ m or more and 10 ⁇ m or less. According to the above configuration, the active material 103 and the solid electrolyte 104 can form a better dispersed state in the electrode.
- the shape of the active material 103 is not limited. That is, the shape of the first active material 101 and the second active material 102 may be, for example, acicular, spherical, ellipsoidal, or the like. The shape of the first active material 101 and the second active material 102 may be, for example, particulate.
- the median diameter of the active material 103 may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the median diameter of the active material 103 is 0.1 ⁇ m or more, the active material 103 and the solid electrolyte 104 can form a good dispersion state in the electrode. This improves the charge/discharge characteristics of the battery.
- the median diameter of the active material 103 is 100 ⁇ m or less, the diffusion rate of lithium inside the active material 103 increases. This allows the battery to operate at high output.
- the median diameter of the active material 103 may be larger than the median diameter of the solid electrolyte 104 . According to the above configuration, the active material 103 and the solid electrolyte 104 can form a good dispersion state in the electrode.
- the median diameter of the first active material 101 may be larger than the median diameter of the second active material 102 .
- the median diameter of first active material 101 may be smaller than the median diameter of second active material 102 .
- the median diameter of first active material 101 may be equal to the median diameter of second active material 102 .
- At least one selected from the group consisting of the first active material 101 and the second active material 102 may be coated with a coating material. Both first active material 101 and second active material 102 may be coated with a coating material. Either one of first active material 101 and second active material 102 may be coated with a coating material.
- a material with low electronic conductivity can be used as the coating material.
- oxide materials, oxide solid electrolytes, and the like can be used as the coating material.
- oxide materials examples include SiO2 , Al2O3 , TiO2 , B2O3 , Nb2O5 , WO3 , and ZrO2 .
- oxide solid electrolytes that can be used as coating materials include Li—Nb—O compounds such as LiNbO 3 , Li—B—O compounds such as LiBO 2 and Li 3 BO 3 , and Li—Al—O compounds such as LiAlO 2 .
- Li--Si--O compounds such as Li 4 SiO 4
- Li--Ti--O compounds such as Li 2 SO 4 and Li 4 Ti 5 O 12
- Li--Zr--O compounds such as Li 2 ZrO 3
- Li 2 Examples include Li--Mo--O compounds such as MoO 3 , Li--VO compounds such as LiV 2 O 5 and Li--WO compounds such as Li 2 WO 4 .
- the coating material may be an oxide solid electrolyte.
- Oxide solid electrolytes have high ionic conductivity. Oxide solid electrolytes have excellent high potential stability. Therefore, by using the oxide solid electrolyte as the coating material, the charge/discharge efficiency of the battery can be further improved.
- the coating material may evenly coat the active material 103 (the first active material 101 and/or the second active material 102). In this case, since direct contact between the active material 103 and the solid electrolyte 104 is suppressed, side reactions of the solid electrolyte 104 can be suppressed. Therefore, the charging and discharging efficiency of the battery can be improved.
- the coating material may partially cover the active material 103 (the first active material 101 and/or the second active material 102). Electron conductivity between particles of the active material 103 is improved by direct contact between the plurality of active materials 103 via portions not having the coating material. Therefore, it is possible to operate the battery at a high output.
- the first active material 101, the second active material 102 and the solid electrolyte 104 may be in contact with each other.
- the electrode material 1000 may include a plurality of first active material 101 particles, a plurality of second active material 102 particles, and a plurality of solid electrolyte 104 particles.
- the content of the active material 103 and the content of the solid electrolyte 104 may be the same or different.
- Electrode material 1000 can be manufactured, for example, by the following method.
- the electrode material 1000 is obtained.
- a method for mixing first active material 101, second active material 102, and solid electrolyte 104 is not particularly limited.
- the first active material 101, the second active material 102, and the solid electrolyte 104 may be mixed using a device such as a mortar, and the first active material 101 and the second active material 102 may be mixed using a mixing device such as a ball mill. and solid electrolyte 104 may be mixed.
- the mixing ratio of first active material 101 and second active material 102 to solid electrolyte 104 is not particularly limited.
- the solid electrolyte 104 can be produced, for example, by the following method.
- Raw material powder is prepared so as to have a compounding ratio of the desired composition.
- the raw material powder may be, for example, a halide.
- LiBr, LiCl, and YCl3 are prepared in a molar ratio of 2.0:1.0:1.0.
- the raw material powders may be mixed in a pre-adjusted molar ratio so as to compensate for composition changes that may occur during the synthesis process.
- the kind of raw material powder is not limited to the above.
- a combination of LiCl and YBr3 , and mixed anion compounds such as LiBr0.5Cl0.5 may be used.
- Mixtures of oxygen-containing raw powders (eg, oxides, hydroxides, sulfates, or nitrates) and halides (eg, ammonium halides) may be used.
- the raw material powder is well mixed using a mortar and pestle, ball mill, or mixer to obtain a mixed powder.
- the mixed powder is pulverized using the method of mechanochemical milling. By doing so, the raw material powder reacts to obtain the solid electrolyte 104 .
- the solid electrolyte 104 may be obtained by sintering the mixed powder in a vacuum or an inert atmosphere after thoroughly mixing the raw material powders.
- Firing may be performed, for example, within the range of 100°C or higher and 650°C or lower for 1 hour or longer. As a result, the above-described solid electrolyte 104 containing a crystalline phase is obtained.
- the composition of the crystal phase in the solid electrolyte 104 (that is, the crystal structure) includes the elements (for example, M and X) constituting the solid electrolyte 104, the ratio of the constituent elements of the solid electrolyte 104, the reaction method between the raw material powders, and can be determined by the choice of reaction conditions.
- Embodiment 2 (Embodiment 2) Embodiment 2 will be described below. Descriptions overlapping those of the first embodiment are omitted as appropriate.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 2000 according to Embodiment 2.
- FIG. 2 is a cross-sectional view showing a schematic configuration of a battery 2000 according to Embodiment 2.
- a battery 2000 in Embodiment 2 includes a first electrode 201 , an electrolyte layer 202 and a second electrode 203 .
- the electrolyte layer 202 is arranged between the first electrode 201 and the second electrode 203 .
- At least one selected from the group consisting of first electrode 201 and second electrode 203 includes electrode material 1000 in the first embodiment.
- FIG. 2 illustrates the case where the second electrode 203 includes electrode material 1000 .
- both charging/discharging efficiency and discharging capacity can be achieved in the battery 2000 .
- the first electrode 201 may be a positive electrode.
- the second electrode 203 is a negative electrode.
- the first electrode 201 may be a negative electrode.
- the second electrode 203 is the positive electrode.
- Both the first electrode 201 and the second electrode 203 may contain the electrode material 1000 .
- Either one of the first electrode 201 and the second electrode 203 may contain the electrode material 1000 .
- the second electrode 203 may contain the electrode material 1000 . That is, the second electrode 203 may contain the active material 103 as a negative electrode active material and the solid electrolyte 104 as a solid electrolyte.
- v1 represents the volume ratio of the active material 103 when the total volume of the active material 103 and the solid electrolyte 104 contained in the first electrode 201 is 100.
- a sufficient energy density of the battery 2000 can be ensured when 30 ⁇ v1 is satisfied.
- v1 ⁇ 95 the battery 2000 can operate at high output.
- v2 represents the volume ratio of the active material 103 when the total volume of the active material 103 and the solid electrolyte 104 contained in the second electrode 203 is 100.
- a sufficient energy density of the battery 2000 can be ensured when 30 ⁇ v2 is satisfied.
- v2 ⁇ 95 the battery 2000 can operate at high output.
- the thickness of the first electrode 201 may be 10 ⁇ m or more and 1000 ⁇ m or less. When the thickness of the first electrode 201 is 10 ⁇ m or more, a sufficient energy density of the battery 2000 can be secured. When the thickness of the first electrode 201 is 1000 ⁇ m or less, the battery 2000 can operate at high output.
- the thickness of the second electrode 203 may be 10 ⁇ m or more and 1000 ⁇ m or less. When the thickness of the second electrode 203 is 10 ⁇ m or more, a sufficient energy density of the battery 2000 can be secured. When the thickness of the second electrode 203 is 1000 ⁇ m or less, the battery 2000 can operate at high output.
- the electrolyte layer 202 is a layer containing an electrolyte.
- the electrolyte is, for example, a solid electrolyte. That is, electrolyte layer 202 may be a solid electrolyte layer.
- a halide solid electrolyte As the solid electrolyte contained in the electrolyte layer 202, a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used.
- the materials exemplified as the solid electrolyte 104 in Embodiment 1 may be used. That is, electrolyte layer 202 may contain a solid electrolyte having the same composition as that of solid electrolyte 104 . According to the above configuration, the charge/discharge efficiency of the battery 2000 can be further improved.
- the electrolyte layer 202 may contain a halide solid electrolyte having a composition different from that of the solid electrolyte 104 .
- the electrolyte layer 202 may contain two or more halogen solid electrolytes selected from the materials listed as the solid electrolyte 104 .
- the electrolyte layer 202 may contain only one halogen solid electrolyte selected from the materials listed as the solid electrolyte 104 .
- Sulfide solid electrolytes include 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 , Li 10 GeP 2 S 12 or the like may be used.
- LiX, Li2O , MOq , LipMOq , etc. may be added to these.
- X includes at least one selected from the group consisting of F, Cl, Br and I.
- M includes at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn.
- p and q are natural numbers respectively.
- One or more sulfide solid electrolytes selected from the above materials may be used.
- oxide solid electrolytes examples include NASICON solid electrolytes typified by LiTi 2 (PO 4 ) 3 and element-substituted products thereof, (LaLi)TiO 3 -based perovskite solid electrolytes, Li 14 ZnGe 4 O 16 , Li LISICON solid electrolytes typified by 4 SiO 4 , LiGeO 4 and elemental substitutions thereof, garnet type solid electrolytes typified by Li 7 La 3 Zr 2 O 12 and their elemental substitutions, Li 3 N and its H substitutions , Li 3 PO 4 and its N-substituted products, LiBO 2 , Li 3 BO 3 and other Li--B--O compounds as a base to which Li 2 SO 4 and Li 2 CO 3 are added, glass, glass ceramics, etc. can be used.
- NASICON solid electrolytes typified by LiTi 2 (PO 4 ) 3 and element-substituted products thereof
- a compound of a polymer compound and a lithium salt can be used.
- the polymer compound may have an ethylene oxide structure.
- a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt. Therefore, the ionic conductivity can be further increased.
- Lithium salts include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN( SO2CF3 ) 2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 ) ( SO2C4F9 ), LiC ( SO2CF3 ) 3 , etc. may be used.
- One or more lithium salts selected from the above lithium salts may be used.
- LiBH 4 --LiI LiBH 4 --P 2 S 5 or the like
- LiBH 4 --LiI LiBH 4 --P 2 S 5 or the like
- the electrolyte layer 202 may contain a solid electrolyte as a main component.
- the electrolyte layer 202 may contain 70% or more of the solid electrolyte in mass ratio with respect to the entire electrolyte layer 202 .
- the electrolyte layer 202 may contain only a solid electrolyte.
- the electrolyte layer 202 may contain two or more of the materials listed above as solid electrolytes.
- the shape of the solid electrolyte contained in the electrolyte layer 202 is not limited.
- the shape of the solid electrolyte may be, for example, acicular, spherical, oval, fibrous, and the like.
- the shape of the solid electrolyte may be, for example, particulate.
- the solid electrolyte may be formed to have a pellet shape or plate shape.
- the median diameter of the solid electrolyte may be 0.1 ⁇ m or more and 100 ⁇ m or less. According to the above configuration, the ionic conductivity of the solid electrolyte can be improved. Also, the solid electrolyte and other materials can form a good dispersion state in the electrolyte layer 202 . Thereby, the charge/discharge characteristics of the battery 2000 are improved.
- the median diameter of the solid electrolyte contained in the electrolyte layer 202 may be 0.5 ⁇ m or more and 10 ⁇ m or less. According to the above configuration, the ionic conductivity of the solid electrolyte can be further improved.
- the thickness of the electrolyte layer 202 may be 1 ⁇ m or more and 1000 ⁇ m or less. When the thickness of the electrolyte layer 202 is 1 ⁇ m or more, the short circuit between the first electrode 201 and the second electrode 203 is less likely to occur. When the thickness of electrolyte layer 202 is 1000 ⁇ m or less, battery 2000 can operate at high output.
- the first electrode 201 may further contain active materials other than the first active material 101 and the second active material 102 .
- the first electrode 201 may contain a positive electrode active material.
- the first electrode 201 may contain only a positive electrode active material as an active material.
- the positive electrode active material includes, for example, a material that has the property of absorbing and releasing metal ions such as lithium ions.
- positive electrode active materials are lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, and transition metal oxynitrides.
- lithium-containing transition metal oxides are Li(Ni,Co,Al) O2 , Li(Ni,Co,Mn) O2 , and LiCoO2 .
- the positive electrode active material may include lithium nickel cobalt manganate.
- the positive electrode active material may be, for example, Li(Ni,Co,Mn) O2 .
- the notation "(A, B, C)" in the chemical formula means "at least one selected from the group consisting of A, B, and C".
- “(Ni, Co, Al)” is synonymous with “at least one selected from the group consisting of Ni, Co, and Al”.
- the first electrode 201 may further contain a solid electrolyte. According to the above configuration, the ionic conductivity of the first electrode 201 can be improved. Thereby, the output characteristics of the battery 2000 can be improved.
- a halide solid electrolyte As the solid electrolyte contained in the first electrode 201, a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used.
- Solid electrolyte contained in the electrolyte layer 202 can be used as the halide solid electrolyte, sulfide solid electrolyte, oxide solid electrolyte, polymer solid electrolyte, or complex hydride solid electrolyte.
- the second electrode 203 may further contain an active material other than the first active material 101 and the second active material 102.
- the second electrode 203 may contain a negative electrode active material.
- the second electrode 203 may contain only the negative electrode active material as an active material.
- the negative electrode active material includes, for example, a material that has a property of intercalating and deintercalating metal ions such as lithium ions.
- Examples of negative electrode active materials are metal materials, carbon materials, oxides, nitrides, tin compounds, and silicon compounds.
- the metal material may be a single metal.
- the metal material may be an alloy.
- Examples of metal materials include lithium metal and lithium alloys.
- Carbon materials include, for example, natural graphite, coke, ungraphitized carbon, carbon fiber, spherical carbon, artificial graphite, and amorphous carbon.
- the second electrode 203 may further contain a solid electrolyte. According to the above configuration, the ionic conductivity of the second electrode 203 can be improved. Thereby, the output characteristics of the battery 2000 can be improved.
- a halide solid electrolyte As the solid electrolyte contained in the second electrode 203, a halide solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a complex hydride solid electrolyte may be used.
- Solid electrolyte contained in the electrolyte layer 202 can be used as the halide solid electrolyte, sulfide solid electrolyte, oxide solid electrolyte, polymer solid electrolyte, or complex hydride solid electrolyte.
- the shape of the solid electrolyte contained in the first electrode 201 and the second electrode 203 is not limited.
- the shape of the solid electrolyte may be, for example, acicular, spherical, oval, fibrous, and the like.
- the shape of the solid electrolyte may be, for example, particulate.
- the solid electrolyte may be formed to have a pellet shape or plate shape.
- the median diameter of the solid electrolyte may be 0.1 ⁇ m or more and 100 ⁇ m or less. According to the above configuration, the positive electrode active material and the solid electrolyte can form a good dispersed state in the first electrode 201 . Also, the negative electrode active material and the solid electrolyte can form a good dispersion state in the second electrode 203 . Thereby, the charge/discharge characteristics of the battery 2000 are improved.
- the median diameter of the solid electrolyte contained in the first electrode 201 and the second electrode 203 may be 0.5 ⁇ m or more and 10 ⁇ m or less. According to the above configuration, the positive electrode active material and the solid electrolyte can form a better dispersed state in the first electrode 201 . Also, the negative electrode active material and the solid electrolyte can form a better dispersed state in the second electrode 203 .
- the shapes of the positive electrode active material and the negative electrode active material are not limited.
- the shape of the positive electrode active material and the negative electrode active material may be, for example, acicular, spherical, oval, or the like.
- the shape of the positive electrode active material and the negative electrode active material may be, for example, particulate.
- the median diameter of the positive electrode active material and the negative electrode active material may be 0.1 ⁇ m or more and 100 ⁇ m or less.
- the median diameter of the positive electrode active material and the negative electrode active material is 0.1 ⁇ m or more, the positive electrode active material and the solid electrolyte can form a good dispersion state in the first electrode 201 .
- the negative electrode active material and the solid electrolyte can form a better dispersed state in the second electrode 203 . Thereby, the charge/discharge characteristics of the battery 2000 are improved.
- the median diameter of the positive electrode active material and the negative electrode active material is 100 ⁇ m or less, the diffusion rate of lithium increases in the first electrode 201 and the second electrode 203 . This allows the battery to operate at high output.
- the median diameters of the positive electrode active material and the negative electrode active material may be larger than the median diameter of the solid electrolyte. According to the above configuration, the positive electrode active material and the solid electrolyte can form a good dispersed state in the first electrode 201 . Also, the negative electrode active material and the solid electrolyte can form a better dispersed state in the second electrode 203 .
- the volume ratio "v3:100-v3" between the positive electrode active material and the solid electrolyte contained in the first electrode 201 may satisfy 30 ⁇ v3 ⁇ 95.
- v3 represents the volume ratio of the positive electrode active material when the total volume of the positive electrode active material and the solid electrolyte contained in the first electrode 201 is 100.
- a sufficient energy density of the battery 2000 can be ensured when 30 ⁇ v3 is satisfied.
- v3 ⁇ 95 the battery 2000 can operate at high output.
- the volume ratio "v4:100-v4" between the negative electrode active material and the solid electrolyte contained in the second electrode 203 may satisfy 30 ⁇ v4 ⁇ 95.
- v4 represents the volume ratio of the negative electrode active material when the total volume of the negative electrode active material and the solid electrolyte contained in the second electrode 203 is 100.
- 30 ⁇ v4 is satisfied, a sufficient energy density of the battery 2000 can be secured.
- v4 ⁇ 95 is satisfied, the battery 2000 can operate at high output.
- At least one selected from the group consisting of the first electrode 201, the electrolyte layer 202, and the second electrode 203 may contain a binder for the purpose of improving adhesion between particles.
- a binder is used to improve the binding properties of the material that constitutes the electrode.
- Binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polyacrylic acid methyl ester, polyacrylic acid ethyl ester, poly Acrylate hexyl ester, polymethacrylic acid, polymethacrylic acid methyl ester, polymethacrylic acid ethyl ester, polymethacrylic acid hexyl ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, Carboxymethyl cellulose etc.
- tetrafluoroethylene hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene.
- Copolymers of two or more materials can also be used as binders. A mixture of two or more selected from the above materials may also be used as the binder.
- At least one of the first electrode 201 and the second electrode 203 may contain a conductive aid for the purpose of increasing electronic conductivity.
- conductive aids include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black and Ketjen black, conductive fibers such as carbon fiber and metal fiber, carbon fluoride, and metal powder such as aluminum.
- conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymeric compounds such as polyaniline, polypyrrole, and polythiophene. Cost reduction can be achieved when a carbon conductive aid is used as the conductive aid.
- the shape of the battery 2000 includes, for example, coin type, cylindrical type, square type, sheet type, button type, flat type, and laminated type.
- Battery 2000 can be manufactured, for example, by the following method. A method for manufacturing battery 2000 will be described below, taking as an example a case where second electrode 203 includes electrode material 1000 in Embodiment 1. FIG.
- a material for forming the first electrode 201, a material for forming the electrolyte layer 202, and an electrode material 1000 as a material for forming the second electrode 203 are prepared respectively.
- a laminate in which the first electrode 201, the electrolyte layer 202, and the second electrode 203 are arranged in this order is produced by a known method. Thus, battery 2000 is obtained.
- the solid electrolyte contained in first electrode 201 and the solid electrolyte contained in electrolyte layer 202 are manufactured by a method similar to the method for manufacturing solid electrolyte 104 described in the method for manufacturing electrode material 1000 in Embodiment 1. sell.
- Example 1>> [Production of solid electrolyte] Under an argon atmosphere with a dew point of ⁇ 60° C. or lower (hereinafter referred to as “dry argon atmosphere”), the raw material powders LiBr, LiCl, LiI, YCl 3 , and YBr 3 were mixed at a molar ratio of Li:Y:Br:Cl: It was weighed so that I 3:1:2:2:2. The raw material powder was pulverized and mixed in a mortar to obtain a mixture. Then, using a planetary ball mill (manufactured by Fritsch, Model P-7), the mixture was milled at 600 rpm for 25 hours. Thus, Li 3 YBr 2 Cl 2 I 2 powder was obtained as the solid electrolyte of Example 1.
- Electrode material Li 4 Ti 5 O 12 (manufactured by Toshima Seisakusho Co., Ltd.) was used as the first active material. MoO 2 (manufactured by Kojundo Chemical Co., Ltd.) was used as the second active material. Vapor-grown carbon fiber (VGCF-H, manufactured by Showa Denko KK) was used as a conductive aid. In a dry argon atmosphere, the solid electrolyte of Example 1, the first active material, the second active material, and the conductive aid were mixed in a mass ratio of 29.7:51.4:17.2:1.7. weighed. These ingredients were mixed in a mortar. Thus, an electrode material of Example 1 was obtained. In the electrode material of Example 1, the mass ratio of the first active material and the second active material was 75:25. "VGCF" is a registered trademark of Showa Denko K.K.
- the obtained electrode material was used as a material for forming the first electrode.
- Li 6 PS 5 Cl manufactured by MSE, which is a solid electrolyte, was used as a material for forming the electrolyte layer. 21.0 mg of electrode material and 80 mg of Li 6 PS 5 Cl were weighed respectively. The electrode material and Li 6 PS 5 Cl were layered in this order in an electrically insulating outer cylinder, and pressure-molded at 720 MPa. Thus, a laminate composed of the first electrode and the electrolyte layer was produced.
- metal In with a thickness of 200 ⁇ m, metal Li with a thickness of 300 ⁇ m, and metal In with a thickness of 200 ⁇ m were arranged in this order on the electrolyte layer of the laminate.
- a three-layer laminate consisting of a first electrode, an electrolyte layer, and an In--Li--In layer was produced.
- stainless steel current collectors were placed on both sides of the three-layer laminate, and current collector leads were attached to each current collector.
- the battery of Example 1 was produced by using an electrically insulating ferrule to shield and seal the inside of the electrically insulating outer cylinder from the outside atmosphere.
- the battery was placed in a constant temperature bath at 25°C.
- the battery was constant current charged at a current value of 115 ⁇ A. Charging was terminated when the potential vs. Li reached 1.0V.
- constant current discharge was performed at a current value of 115 ⁇ A, and the discharge was terminated when the potential against Li reached 2.5V. Based on the above charge/discharge results, the discharge capacity at 115 ⁇ A discharge was obtained, and the charge/discharge efficiency at 115 ⁇ A charge/discharge was calculated. The results are shown in Table 1.
- the discharge capacity increased as the ratio of the mass of the second active material to the total mass of the first active material and the second active material increased. As the ratio of the mass of the second active material to the total mass of the first active material and the second active material increased, the charge/discharge efficiency decreased.
- MoO 2 as the second active material reversibly reacts with lithium in the same potential range as Li 4 Ti 5 O 12 as the first active material.
- the density and mass capacity of MoO 2 are 6.47 g/cm 3 and 209 mAh/g. Therefore, MoO 2 has a higher energy density per volume compared to Li 4 Ti 5 O 12 . Therefore, by substituting MoO 2 for a portion of Li 4 Ti 5 O 12 , the energy density per volume of the battery could be increased. As a result, the discharge capacity per mass of the battery was able to be improved.
- MoO 2 has a lower charge-discharge efficiency than Li 4 Ti 5 O 12 . Therefore, the charge/discharge efficiency of the battery decreased as the mass ratio of the second active material increased.
- Li 4 Ti 5 O 12 as the first active material has less expansion and contraction due to insertion and extraction of lithium ions than MoO 2 as the second active material. Therefore, in Example 1, in which the ratio of the mass of the first active material to the total mass of the first active material and the second active material is 75%, both the charge and discharge efficiency and the discharge capacity of the battery are achieved. Compared to 2, the safety of the battery could be further improved.
- Example 4 [Production of solid electrolyte]
- the raw material powder was pulverized and mixed in a mortar to obtain a mixture.
- using a planetary ball mill manufactured by Fritsch, Model P-7
- the mixture was milled at 600 rpm for 25 hours.
- powder of Li 3 YBr 2 Cl 4 was obtained as the solid electrolyte of Example 4.
- Li(Ni, Co, Mn)O 2 was used as a positive electrode active material.
- Vapor-grown carbon fiber (VGCF-H, manufactured by Showa Denko KK) was used as a conductive aid.
- the positive electrode active material, the solid electrolyte of Example 4, and the conductive aid were weighed out in a mass ratio of 83:16:1. These ingredients were mixed in a mortar. Thus, a positive electrode material of Example 4 was obtained.
- the electrode material of Example 1 was used as the negative electrode material. 14.0 mg of the negative electrode material, 80 mg of the solid electrolyte of Example 4, and 8.5 mg of the positive electrode material were weighed respectively. The negative electrode material, the solid electrolyte of Example 4, and the positive electrode material were laminated in this order in an electrically insulating outer cylinder, and pressure-molded at 720 MPa. Thus, a laminate composed of the positive electrode, the electrolyte layer and the negative electrode was produced. Next, collectors made of stainless steel were arranged on both sides of the laminate, and collector leads were attached to each collector. Finally, the battery of Example 4 was produced by using an electrically insulating ferrule to isolate and seal the inside of the electrically insulating outer cylinder from the outside atmosphere.
- the battery was placed in a constant temperature bath at 25°C.
- the battery was constant current charged at a current value of 64 ⁇ A. Charging was terminated when the potential vs. Li reached 2.75V.
- constant current discharge was performed at a current value of 64 ⁇ A, and the discharge was terminated when the potential against Li reached 0.95V. Results are shown in FIG.
- ⁇ Consideration ⁇ 3 is a graph showing the results of an initial charge/discharge test of the battery in Example 4.
- FIG. 3 the vertical axis indicates voltage (V), and the horizontal axis indicates capacity per mass (arbitrary unit).
- Li 3 YBr 2 Cl 4 was used as the solid electrolyte contained in the positive electrode material and the solid electrolyte for the electrolyte layer.
- Li3YBr2Cl2I2 was used as the solid electrolyte contained in the negative electrode material.
- a solid electrolyte containing Li, M, and X was used as the solid electrolyte.
- M is at least one selected from the group consisting of metal elements other than Li and metalloid elements
- X is at least one selected from the group consisting of F, Cl, Br, and I.
- the battery of the present disclosure can be used, for example, as an all-solid lithium secondary battery.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
Li、Ti、およびOを含む第1活物質と、
MoおよびOを含む第2活物質と、
固体電解質と、
を含む。
特許文献1には、負極活物質としてチタン酸リチウムを含む負極材料を用いた電池が開示されている。チタン酸リチウムを用いた電池は、高い充放電効率を示すことが知られている。また、チタン酸リチウムは、リチウム金属の析出を発生させにくい。そのため、チタン酸リチウムを負極に用いると、析出した金属が電解質層を貫通して正極と接触することによる内部短絡を防止することができる。さらに、チタン酸リチウムには、リチウムイオンの挿入および脱離に伴う膨張および収縮が小さいという特徴がある。したがって、活物質としてチタン酸リチウムを用いると、電池の安全性を向上させることができる。一方で、チタン酸リチウムには、質量あたりの容量が小さいという問題がある。
本開示の第1態様に係る電極材料は、
Li、Ti、およびOを含む第1活物質と、
MoおよびOを含む第2活物質と、
固体電解質と、
を含む。
LiαMβXγ ・・・式(1)
ここで、α、β、およびγは、それぞれ独立して0より大きい値である。以上の構成によれば、電池の出力特性をより向上させることができる。
第1電極、第2電極、および前記第1電極と前記第2電極との間に配置された電解質層を備え、
前記第1電極および前記第2電極からなる群より選ばれる少なくとも1つは、第1から第11態様のいずれか1つに係る電極材料を含む。
図1は、実施の形態1における電極材料1000の概略構成を示す断面図である。
電極材料1000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。実施の形態1と重複する説明は、適宜、省略される。
電池2000は、例えば、下記の方法によって製造されうる。以下では、第2電極203が実施の形態1における電極材料1000を含む場合を例として、電池2000の製造方法を説明している。
[固体電解質の作製]
露点-60℃以下のアルゴン雰囲気(以下、「乾燥アルゴン雰囲気」と称する)下で、原料粉であるLiBr、LiCl、LiI、YCl3、およびYBr3をモル比でLi:Y:Br:Cl:I=3:1:2:2:2となるように秤量した。原料粉を乳鉢で粉砕および混合して混合物を得た。その後、遊星型ボールミル(フリッチュ社製,P-7型)を用い、25時間、600rpmの条件で混合物をミリング処理した。これにより、実施例1の固体電解質としてLi3YBr2Cl2I2の粉末を得た。
第1活物質としてLi4Ti5O12(豊島製作所社製)を用いた。第2活物質としてMoO2(高純度化学社製)を用いた。導電助剤として気相法炭素繊維(昭和電工社製,VGCF-H)を用いた。乾燥アルゴン雰囲気下で、実施例1の固体電解質、第1活物質、第2活物質、および導電助剤を質量比率で29.7:51.4:17.2:1.7となるように秤量した。これらの材料を乳鉢で混合した。これにより、実施例1の電極材料を得た。実施例1の電極材料において、第1活物質と第2活物質の質量比率は、75:25であった。なお、「VGCF」は、昭和電工株式会社の登録商標である。
第1電極の形成用の材料として、得られた電極材料を用いた。電解質層の形成用の材料として、固体電解質であるLi6PS5Cl(MSE社製)を用いた。21.0mgの電極材料と80mgのLi6PS5Clとをそれぞれ秤量した。電気的絶縁性の外筒の中に電極材料およびLi6PS5Clをこの順に積層し、720MPaで加圧成形した。これにより、第1電極と電解質層からなる積層体を作製した。次に、積層体の電解質層の上に、厚み200μmの金属In、厚み300μmの金属Li、および厚み200μmの金属Inをこの順に配置した。これを80MPaの圧力で加圧成形することで、第1電極、電解質層、およびIn-Li-In層からなる3層積層体を作製した。次に、3層積層体の両面にステンレス鋼製の集電体を配置し、各集電体に集電リードを付設した。最後に、電気的絶縁性のフェルールを用いて、電気的絶縁性の外筒の内部を外気雰囲気から遮断および密閉することで、実施例1の電池を作製した。
電極材料の作製において、固体電解質、第1活物質、第2活物質、および導電助剤を質量比率で26.9:35.8:35.8:1.5となるように秤量した。これ以外は実施例1と同様の方法により、実施例2の電極材料および電池を作製した。実施例2の電極材料において、第1活物質と第2活物質の質量比率は、50:50であった。
電極材料の作製において、第2活物質(MoO2)は用いなかった。すなわち、比較例1の電極材料において、第1活物質と第2活物質の質量比率は、100:0であった。固体電解質、第1活物質、および導電助剤を質量比率で32.3:65.8:1.9となるように秤量した。これ以外は実施例1と同様の方法により、比較例1の電極材料および電池を作製した。
電極材料の作製において、第1活物質(Li4Ti5O12)は用いなかった。すなわち、比較例1の電極材料において、第1活物質と第2活物質の質量比率は、0:100であった。固体電解質、第2活物質、および導電助剤を質量比率で20.4:78.4:1.2となるように秤量した。これ以外は実施例1と同様の方法により、比較例2の電極材料および電池を作製した。
実施例1の固体電解質について、ICP(Inductively coupled Plasma)発光分光分析法を用いて組成の評価を行った。Li/Yの仕込み組成からのずれは3%以内であった。この結果から、遊星型ボールミルによる仕込み組成と、得られた固体電解質の組成とはほとんど同じであったといえる。
次に、実施例1から2および比較例1から2の電池を用いて、以下の条件で、充放電試験を実施した。
表1に示されるように、活物質として第1活物質および第2活物質を含む実施例1および2では、放電容量および充放電効率のいずれもが高い数値を示していた。このように、実施例1および2では、充放電効率と放電容量とを両立できた。
[固体電解質の作製]
乾燥アルゴン雰囲気下で、原料粉であるLiBr、YBr3、LiCl、およびYCl3をモル比でLi:Y:Br:Cl=3:1:2:4となるように秤量した。原料粉を乳鉢で粉砕および混合して混合物を得た。その後、遊星型ボールミル(フリッチュ社製,P-7型)を用い、25時間、600rpmの条件で混合物をミリング処理した。これにより、実施例4の固体電解質としてLi3YBr2Cl4の粉末を得た。
正極活物質として、Li(Ni,Co,Mn)O2を用いた。導電助剤として気相法炭素繊維(昭和電工社製,VGCF-H)を用いた。乾燥アルゴン雰囲気下で、正極活物質、実施例4の固体電解質、および導電助剤を質量比率で83:16:1となるように秤量した。これらの材料を乳鉢で混合した。これにより、実施例4の正極材料を得た。
負極材料として、実施例1の電極材料を用いた。14.0mgの負極材料と、80mgの実施例4の固体電解質と、8.5mgの正極材料とをそれぞれ秤量した。電気的絶縁性の外筒の中に負極材料、実施例4の固体電解質、および正極材料をこの順に積層し、720MPaで加圧成形した。これにより、正極、電解質層および負極からなる積層体を作製した。次に、積層体の両面にステンレス鋼製の集電体を配置し、各集電体に集電リードを付設した。最後に、電気的絶縁性のフェルールを用いて、電気的絶縁性の外筒の内部を外気雰囲気から遮断および密閉することで、実施例4の電池を作製した。
次に、実施例4の電池を用いて、以下の条件で、充放電試験を実施した。
図3は、実施例4における電池の初期の充放電試験の結果を示すグラフである。図3において、縦軸は電圧(V)を示し、横軸は質量あたりの容量(任意単位)を示す。実施例4では、正極材料に含まれる固体電解質、および電解質層用の固体電解質として、Li3YBr2Cl4を用いた。負極材料に含まれる固体電解質として、Li3YBr2Cl2I2を用いた。このように、実施例4における電池では、固体電解質として、Li、M、およびXを含む固体電解質が用いられた。なお、Mは、Li以外の金属元素および半金属元素からなる群より選ばれる少なくとも1つであり、Xは、F、Cl、Br、およびIからなる群より選ばれる少なくとも1つである。図3に示された結果から、固体電解質としてこのような材料のみが使用された電池は、安定動作が可能であることが確認された。また、実施例4による電池では、固体電解質に硫黄が含まれていなかった。したがって、実施例4による電池では、硫化水素ガスの発生を抑制でき、電池の安全性が向上した。
101 第1活物質
102 第2活物質
103 活物質
104 固体電解質
2000 電池
201 第1電極
202 電解質層
203 第2電極
Claims (12)
- Li、Ti、およびOを含む第1活物質と、
MoおよびOを含む第2活物質と、
固体電解質と、
を含む、
電極材料。 - 前記第1活物質および前記第2活物質の合計の質量に対する前記第1活物質の質量の比率は、50%以上かつ99%以下である、
請求項1に記載の電極材料。 - 前記比率は、70%以上かつ95%以下である、
請求項2に記載の電極材料。 - 前記第1活物質は、リチウムチタン酸化物を含む、
請求項1から3のいずれか一項に記載の電極材料。 - 前記リチウムチタン酸化物は、Li4Ti5O12を含む、
請求項4に記載の電極材料。 - 前記第2活物質は、モリブデン酸化物を含む、
請求項1から5のいずれか一項に記載の電極材料。 - 前記モリブデン酸化物は、MoO2を含む、
請求項6に記載の電極材料。 - 前記固体電解質は、Li、M、およびXを含み、
Mは、Li以外の金属元素および半金属元素からなる群より選ばれる少なくとも1つであり、
Xは、F、Cl、Br、およびIからなる群より選ばれる少なくとも1つである、
請求項1から7のいずれか一項に記載の電極材料。 - 前記固体電解質は、下記の組成式(1)により表され、
LiαMβXγ ・・・式(1)
ここで、α、β、およびγは、それぞれ独立して0より大きい値である、
請求項8に記載の電極材料。 - 前記固体電解質は、Li3YBr2Cl2I2を含む、
請求項9に記載の電極材料。 - 前記固体電解質は、硫黄を含まない、
請求項8から10のいずれか一項に記載の電極材料。 - 第1電極、第2電極、および前記第1電極と前記第2電極との間に配置された電解質層を備え、
前記第1電極および前記第2電極からなる群より選ばれる少なくとも1つは、請求項1から11のいずれか一項に記載の電極材料を含む、
電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023525381A JPWO2022254796A1 (ja) | 2021-05-31 | 2022-02-08 | |
CN202280034725.5A CN117296165A (zh) | 2021-05-31 | 2022-02-08 | 电极材料及电池 |
US18/500,514 US20240063378A1 (en) | 2021-05-31 | 2023-11-02 | Electrode material and battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021091878 | 2021-05-31 | ||
JP2021-091878 | 2021-05-31 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/500,514 Continuation US20240063378A1 (en) | 2021-05-31 | 2023-11-02 | Electrode material and battery |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022254796A1 true WO2022254796A1 (ja) | 2022-12-08 |
Family
ID=84324124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/004783 WO2022254796A1 (ja) | 2021-05-31 | 2022-02-08 | 電極材料および電池 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240063378A1 (ja) |
JP (1) | JPWO2022254796A1 (ja) |
CN (1) | CN117296165A (ja) |
WO (1) | WO2022254796A1 (ja) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007227358A (ja) * | 2006-01-24 | 2007-09-06 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2009099522A (ja) * | 2007-09-25 | 2009-05-07 | Sanyo Electric Co Ltd | 非水電解質二次電池用活物質及びそれを用いた非水電解質二次電池 |
JP2010086896A (ja) * | 2008-10-02 | 2010-04-15 | Sanyo Electric Co Ltd | 非水電解質二次電池及び非水電解質二次電池用活物質 |
WO2019146295A1 (ja) * | 2018-01-26 | 2019-08-01 | パナソニックIpマネジメント株式会社 | 負極材料およびそれを用いた電池 |
-
2022
- 2022-02-08 JP JP2023525381A patent/JPWO2022254796A1/ja active Pending
- 2022-02-08 CN CN202280034725.5A patent/CN117296165A/zh active Pending
- 2022-02-08 WO PCT/JP2022/004783 patent/WO2022254796A1/ja active Application Filing
-
2023
- 2023-11-02 US US18/500,514 patent/US20240063378A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007227358A (ja) * | 2006-01-24 | 2007-09-06 | Sanyo Electric Co Ltd | 非水電解質二次電池 |
JP2009099522A (ja) * | 2007-09-25 | 2009-05-07 | Sanyo Electric Co Ltd | 非水電解質二次電池用活物質及びそれを用いた非水電解質二次電池 |
JP2010086896A (ja) * | 2008-10-02 | 2010-04-15 | Sanyo Electric Co Ltd | 非水電解質二次電池及び非水電解質二次電池用活物質 |
WO2019146295A1 (ja) * | 2018-01-26 | 2019-08-01 | パナソニックIpマネジメント株式会社 | 負極材料およびそれを用いた電池 |
Also Published As
Publication number | Publication date |
---|---|
US20240063378A1 (en) | 2024-02-22 |
JPWO2022254796A1 (ja) | 2022-12-08 |
CN117296165A (zh) | 2023-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7182196B2 (ja) | 電池 | |
JP7199038B2 (ja) | 負極材料およびそれを用いた電池 | |
JP7182114B2 (ja) | 固体電解質材料、および、電池 | |
JP7349645B2 (ja) | 電極材料、および、電池 | |
JP7316564B2 (ja) | 電池 | |
JP7145439B2 (ja) | 電池 | |
JP7249562B2 (ja) | 電池 | |
WO2019135346A1 (ja) | 正極材料、および、電池 | |
WO2019135322A1 (ja) | 正極材料、および、電池 | |
JP7217432B2 (ja) | 正極材料およびそれを用いた電池 | |
WO2019146296A1 (ja) | 正極材料およびそれを用いた電池 | |
WO2022224505A1 (ja) | 正極材料および電池 | |
WO2023021836A1 (ja) | 電極および電池 | |
WO2021157361A1 (ja) | 正極材料および電池 | |
WO2020174868A1 (ja) | 正極材料、および、電池 | |
WO2023286614A1 (ja) | 正極材料および電池 | |
WO2022244445A1 (ja) | 被覆正極活物質、正極材料および電池 | |
US20240097123A1 (en) | Electrode material and battery | |
WO2023032473A1 (ja) | 正極材料および電池 | |
WO2022254796A1 (ja) | 電極材料および電池 | |
WO2022264554A1 (ja) | 複合活物質、電極材料、電池、および複合活物質の製造方法 | |
WO2022219842A1 (ja) | 負極材料およびそれを用いた電池 | |
WO2022219843A1 (ja) | 電池 | |
WO2022264555A1 (ja) | 電極材料および電池 | |
WO2023132304A1 (ja) | 正極材料および電池 |
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: 22815555 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023525381 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280034725.5 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: 22815555 Country of ref document: EP Kind code of ref document: A1 |