WO2023276281A1 - 層状複水酸化物、層状複水酸化物の製造方法、空気極および金属空気二次電池 - Google Patents
層状複水酸化物、層状複水酸化物の製造方法、空気極および金属空気二次電池 Download PDFInfo
- Publication number
- WO2023276281A1 WO2023276281A1 PCT/JP2022/009438 JP2022009438W WO2023276281A1 WO 2023276281 A1 WO2023276281 A1 WO 2023276281A1 JP 2022009438 W JP2022009438 W JP 2022009438W WO 2023276281 A1 WO2023276281 A1 WO 2023276281A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ldh
- separator
- metal
- layered double
- solution
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 40
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000012736 aqueous medium Substances 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000010410 layer Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- -1 hydroxide ions Chemical class 0.000 description 18
- 239000000758 substrate Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 230000006870 function Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000004020 conductor Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 210000001787 dendrite Anatomy 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000005588 protonation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- 229910002429 LaSr3Fe3O10 Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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 invention relates to a layered double hydroxide, a method for producing a layered double hydroxide, an air electrode, and a metal-air secondary battery.
- a metal-air secondary battery is a secondary battery in which a metal is used for the negative electrode and oxygen and/or water in the air is used for the positive electrode as an active material.
- ORR oxygen reduction reaction
- OER oxygen evolution reaction
- a layered double hydroxide (layered hydroxide) having a plurality of hydroxide layers and an intermediate layer interposed between the hydroxide layers is used for various applications as disclosed in Patent Document 1.
- Double Hydroxide (LDH) is attracting attention.
- binary LDHs such as Ni--Fe-based LDHs and Ni--Co-based LDHs have been put to practical use as catalysts for air electrodes, but LDHs still have much room for improvement as catalysts. ing.
- the present invention has been made to solve the above conventional problems, and its main purpose is to provide a layered double hydroxide having excellent catalytic function (for example, oxygen evolution catalytic function).
- a layered double hydroxide according to an embodiment of the present invention contains the four elements Ni, Fe, V and Co, and further contains Mn as the fifth element.
- the atomic ratio of (Ni + Mn)/(Ni + Fe + V + Co + Mn) determined by energy dispersive X-ray spectroscopy (EDS) of the layered double hydroxide is 0.6 or more and 0.8 or less. be.
- the atomic ratio of Mn/Ni of the layered double hydroxide determined by energy dispersive X-ray spectroscopy (EDS) is 0.2 or more and 0.8 or less.
- the atomic ratio of Mn/(Ni+Fe+V+Co+Mn) determined by energy dispersive X-ray spectroscopy (EDS) of the layered double hydroxide is greater than 0 and 0.4 or less.
- EDS energy dispersive X-ray spectroscopy
- a method for producing the layered double hydroxide comprises preparing a solution in which salts of Ni, Fe, V, Co and Mn are respectively dissolved in a predetermined molar ratio in an aqueous medium, adding acetylacetone during or after preparation of the solution, adding propylene oxide to the acetylacetone-added solution; and allowing the propylene oxide-added solution to stand for a predetermined time.
- the production method includes leaving the propylene oxide-added solution for a predetermined time to obtain a gel, and leaving the gel for a predetermined time to obtain a sol.
- a cathode is provided.
- the air electrode has a porous current collector and a catalyst layer that covers at least a portion of the porous current collector and contains the layered double hydroxide.
- a metal-air secondary battery is provided. This metal-air secondary battery has the air electrode, the separator, the electrolytic solution, and the metal negative electrode.
- the separator is a hydroxide ion conductive dense separator, and the electrolyte is separated from the air electrode by the separator.
- the layered double hydroxide contains the four elements of Ni, Fe, V and Co, so that an excellent catalytic function can be achieved.
- FIG. 1 is a schematic diagram showing a schematic configuration of a metal-air secondary battery according to one embodiment of the present invention
- FIG. 2 is an enlarged view showing an example of a portion of the air electrode of the metal-air secondary battery shown in FIG. 1
- FIG. 2 is a cross-sectional view conceptually showing an example of a separator (hydroxide ion conductive dense separator) of the metal-air secondary battery shown in FIG. 1.
- FIG. 1 is an X-ray diffraction pattern of Example 1.
- FIG. 1 is an SEM image and an elemental map image of Example 1.
- FIG. 4 is a graph showing a comparison between Example 1, Comparative Example 1, and Comparative Example 3 regarding the relationship between the potential and current density with respect to the hydrogen electrode.
- Layered Double Hydroxide A layered double hydroxide (LDH) according to an embodiment of the present invention comprises the four elements Ni, Fe, V and Co. Specifically, it may be LDH in which at least these four elements are combined.
- excellent catalytic function for example, oxygen generating catalytic function
- the rising potential (on-set potential) can be lowered and / or the potential at a predetermined current density It can be made low (low resistance).
- the above LDH may contain at least one fifth element selected from the group consisting of Mn, Al, Zn, W, Cr and Ru in addition to the above four elements. Specifically, it may be LDH complexed with at least the fifth element. By containing the fifth element, even better catalytic function (for example, oxygen evolution catalytic function) can be achieved.
- catalytic function for example, oxygen evolution catalytic function
- the atomic ratio of (Ni + Fe + V + Co) or the atomic ratio of Ni / (Ni + Fe + V + Co + fifth element) is preferably 0.3 or more and 0.8 or less, more preferably 0.35 or more and 0.75 or less, and still more preferably It is 0.4 or more and 0.7 or less.
- the atomic ratio of Fe / (Ni + Fe + V + Co) or the atomic ratio of Fe / (Ni + Fe + V + Co + fifth element) is preferably greater than 0 and 0.3 or less, more preferably 0.005 or more and 0.25 or less, and further It is preferably 0.01 or more and 0.2 or less.
- the atomic ratio of V/(Ni + Fe + V + Co) or the atomic ratio of V / (Ni + Fe + V + Co + fifth element) is preferably 0.04 or more and 0.49 or less, more preferably 0.06 or more and 0.35 or less, and further It is preferably 0.07 or more and 0.3 or less.
- the atomic ratio of Co/(Ni+Fe+V+Co) or the atomic ratio of Co/(Ni+Fe+V+Co+the fifth element) is preferably greater than 0 and 0.2 or less, more preferably 0.005 or more and 0.18 or less, and further It is preferably 0.01 or more and 0.17 or less. According to such a range, even better catalytic function (for example, oxygen generating catalytic function) can be realized.
- the LDH contains at least Mn as the fifth element.
- Mn the atomic ratio of Mn/(Ni+Fe+V+Co+Mn) is preferably greater than 0 and 0.4 or less, more preferably 0.05 or more and 0.35 or less, and still more preferably 0.1 or more and 0 .3 or less.
- M 2+ is at least one divalent cation
- M 3+ is at least one trivalent cation
- a n- is an n-valent anion
- n is 1 or more.
- m is any real number (greater than 0).
- M 2+ may include Ni 2+ and Mn 2+ .
- M 3+ may include Fe 3+ , V 3+ and Co 3+ .
- the atomic ratio of (Ni+Mn)/(Ni+Fe+V+Co+Mn) is preferably 0.6 or more.
- the atomic ratio of (Ni+Mn)/(Ni+Fe+V+Co+Mn) is preferably 0.8 or less, more preferably 0.75 or less, and still more preferably 0.7 or less.
- the Mn/Ni atomic ratio is preferably 0.2 or more and 0.8 or less, more preferably 0.25 or more and 0.75 or less, and still more preferably 0.3 or more and 0.7 or less.
- the LDH contains at least Al as the fifth element.
- the atomic ratio of Al/(Ni + Fe + V + Co + Al) is preferably greater than 0 and 0.2 or less, more preferably 0.005 or more and 0.15 or less, still more preferably 0.01 or more and 0 .1 or less.
- the LDH contains at least Zn as the fifth element.
- the atomic ratio of Zn/(Ni + Fe + V + Co + Zn) is preferably greater than 0 and 0.3 or less, more preferably 0.005 or more and 0.25 or less, still more preferably 0.01 or more and 0 .2 or less.
- the above ratio can be determined by composition analysis using energy dispersive X-ray spectroscopy (EDS).
- EDS energy dispersive X-ray spectroscopy
- composition analysis is performed using an energy dispersive X-ray spectrometer (eg, X-act, manufactured by Oxford Instruments), and the ratio (atomic ratio) can be calculated from the analysis results.
- the LDH can have multiple hydroxide layers and intermediate layers interposed between the hydroxide layers.
- the hydroxide layer contains constituent elements (typically in ionic form) and OH groups
- the intermediate layer contains anions and H2O .
- the anion is any suitable anion with a valence of 1 or higher. Specific examples of anions include halide ions such as NO 3 ⁇ , CO 3 2 ⁇ , SO 4 2 ⁇ , OH ⁇ , and Cl ⁇ . CO 3 2- , OH - and Cl - are preferred.
- the intermediate layer may contain one type of anion, or may contain two or more types of anions.
- the LDH is particulate.
- the LDH is plate-like particles and can have any suitable planar shape.
- planar view shapes include circular, elliptical, rectangular, triangular, polygonal, and irregular shapes.
- the size of the LDH (longer diameter of primary particles) is, for example, 1 nm to 0.2 ⁇ m, and the thickness is, for example, 0.5 nm to 50 nm.
- the "size of LDH” refers to the size of the LDH in plan view, for example, the diameter in the case of a circle, the length of the major axis in the case of an ellipse, and the length of the long side in the case of a rectangle.
- the size and thickness of LDH can be measured, for example, by scanning electron microscope (SEM) observation.
- the LDH can be produced by any appropriate method.
- the LDH can be produced by a so-called sol-gel method.
- the method for producing LDH includes dissolving salts of Ni, Fe, V, Co and, if necessary, the fifth element (Mn in one embodiment) in an aqueous medium at a predetermined molar ratio. adding acetylacetone (to said aqueous medium or said solution) during or after the preparation of the solution; adding propylene oxide to the solution to which acetylacetone has been added; and to the solution to which propylene oxide has been added. leaving for a predetermined time;
- Salts include, for example, nitrates, carbonates, sulfates, hydroxides, halides (chlorides, iodides, bromides, fluorides).
- a chloride is used as the salt.
- Chlorides are inexpensive, readily available, and highly soluble in an aqueous medium, which will be described later.
- Salts of the constituent elements may be salts of the same kind (for example, chlorides) or salts of different kinds.
- the valence (number of valences) of the constituent elements may be the same or different between the valence in the raw material (salt) and the valence in the resulting LDH.
- CoCl 2 may be employed as the Co starting material (salt), and Co may take the form of Co 3+ in the resulting LDH.
- feed ratio The amount of salt of the constituent elements used (feed ratio) is adjusted, for example, according to the target LDH composition.
- the aqueous medium typically contains water.
- water for example, tap water, ion-exchanged water, pure water, and ultrapure water are used. Ultrapure water is preferred. Since ultrapure water has very few impurities, for example, LDH with very few impurities can be obtained with very little influence on the reaction.
- the aqueous medium may contain a hydrophilic organic solvent.
- hydrophilic organic solvents include alcohols such as ethanol and methanol.
- the hydrophilic organic solvent can be used preferably in the range of 100 to 200 parts by weight with respect to 100 parts by weight of water.
- the stirring time is, for example, 5 minutes to 30 minutes.
- acetylacetone to the aqueous medium or the solution.
- acetylacetone may be added during preparation of the solution or after preparation of the solution.
- spontaneous gelation and subsequent spontaneous disaggregation which will be described later, can be achieved, and as a result, fine-particle LDH can be obtained (aggregation and/or sedimentation can be suppressed).
- fine-particle LDH can be obtained (aggregation and/or sedimentation can be suppressed). can. That is, it is possible to achieve both growth and stabilization of LDH particles, which are in a trade-off relationship.
- the amount of acetylacetone added is preferably 0.008% to 0.036% (molar ratio), more preferably 0.016% to 0.018% (molar ratio), relative to the total amount of the constituent elements. be. If the amount of acetylacetone added is within this range, for example, LDH with extremely few impurities can be obtained.
- the stirring time is, for example, 15 minutes to 60 minutes.
- Propylene oxide is added to the solution to which acetylacetone has been added.
- Propylene oxide can function as a proton scavenger through protonation of the epoxy oxygen and subsequent ring opening by nucleophilic substitution of the conjugate base. Such protonation and ring-opening increase the pH of the solution and may promote crystallization (eg, particulate formation) of LDH by co-precipitation.
- the amount of propylene oxide added is preferably 0.12% to 0.48% (molar ratio), more preferably 0.23% to 0.25% (molar ratio), relative to the total amount of the constituent elements. is.
- the solution to which the propylene oxide is added is left for a predetermined time (for example, 12 hours to 36 hours).
- the production method may include leaving a solution to which propylene oxide has been added for a predetermined period of time to obtain a gel; and leaving the obtained gel for a predetermined period of time to obtain a sol.
- the solution may gel after the addition of propylene oxide. Specifically, gels containing complexes of constituent elements can be formed. Substantially, at this point, LDH is formed as a complex, and it is presumed that this LDH aggregates to form a gel.
- the standing time until gel formation is, for example, 1 to 6 hours, preferably 2 to 4 hours. If desired, the solution may be stirred briefly (eg, 30 seconds to 2 minutes) before standing (ie, immediately after the propylene oxide is added).
- the gel formed above is left for a predetermined time.
- the gel can be deagglomerated to form a sol containing LDH particles (eg, platelet microparticles).
- LDH particles eg, platelet microparticles.
- the standing time until sol formation is, for example, 5 hours or longer, preferably 6 to 30 hours.
- the sol can be subjected to drying treatment. Drying may be performed at room temperature (around 23° C.) from the viewpoint of suppressing aggregation of the obtained particles, or may be performed using a dryer. In the latter case, the drying temperature is preferably 60°C to 90°C, more preferably 70°C to 80°C. Moreover, drying may be performed under reduced pressure (for example, vacuum drying). In addition, each of the above steps can be performed at room temperature (around 23° C.).
- sol-gel method can be performed according to the method described in ACS Nano 2016, 10, 5550-5559. The description of the document is incorporated herein by reference.
- the production of LDH by the sol-gel method is performed in the presence of a substrate (eg, porous sheet).
- a substrate eg, porous sheet
- LDH is produced while the substrate is immersed in the aqueous medium.
- the porous sheet can correspond to a porous current collector of an air electrode, which will be described later. Therefore, this embodiment can also be a method for manufacturing an air electrode.
- the production of LDH and the binding and/or attachment of LDH to the porous current collector can occur simultaneously.
- the LDH can be produced by a coprecipitation method.
- the method for producing LDH includes dropping a raw material aqueous solution containing constituent elements into an aqueous solution containing carbonate ions under a condition of pH 9.5 to 12 for reaction.
- a condition of pH 9.5 to 12 for reaction for pH adjustment, for example, an aqueous NaOH solution is used.
- the resulting reactant is allowed to grow, for example by stirring for a period of time, as required.
- LDH particles may be obtained by drying and/or pulverizing the resulting reactant.
- Confirmation of the production of LDH can be performed, for example, by X-ray diffraction measurement.
- the first peak is in the range of the diffraction angle 2 ⁇ of 10° to 12°
- the second peak is in the range of the diffraction angle 2 ⁇ of 22° to 24°
- the diffraction angle 2 ⁇ is 33°.
- a third peak can be detected within ⁇ 35°.
- the first peak can correspond to the (003) peak of LDH
- the second peak can correspond to the (006) peak of LDH
- the third peak can correspond to the (012) peak of LDH.
- the LDH contains the four elements of Ni, Fe, V and Co, and the fifth element, so that it can be produced regardless of the production method (for example, a sol-gel method or a coprecipitation method). ), excellent catalytic function (for example, oxygen evolution catalytic function) can be realized.
- FIG. 1 is a schematic diagram showing a schematic configuration of a metal-air secondary battery according to one embodiment of the present invention.
- the metal-air secondary battery 10 has an air electrode (positive electrode) 12, a metal negative electrode 14, a separator 16 disposed between the air electrode 12 and the metal negative electrode 14, and an electrolytic solution 18, which are contained in a container. 20 is housed.
- the air electrode 12 is accommodated in the container 20 so as to be in contact with the outside air.
- the separator 16 is provided adjacent to the air electrode 12 , and the electrolytic solution 18 is isolated from the air electrode 12 by the separator 16 .
- a metal negative electrode 14 is immersed in an electrolytic solution 18 .
- Metal anode 14 may be composed of any suitable metal. Typically, metal anode 14 comprises zinc or a zinc alloy.
- the metal-air secondary battery 10 is a zinc-air secondary battery.
- the electrolytic solution 18 a strongly alkaline aqueous solution (for example, an aqueous potassium hydroxide solution) having a pH of about 14 is typically used.
- FIG. 2 is an enlarged view showing an example of a part of the air electrode of the metal-air secondary battery shown in FIG.
- the air electrode 12 includes a porous current collector 12a and a catalyst layer 12b covering the surface of the porous current collector 12a.
- the catalyst layer 12b contains the LDH.
- Porous current collectors can typically be composed of an electrically conductive material with gas diffusion properties. Specific examples of such conductive materials include carbon, nickel, stainless steel, titanium, and combinations thereof. Carbon is preferred. Specific configurations of the porous current collector include carbon paper, nickel foam, stainless steel non-woven fabric, and combinations thereof. Carbon paper is preferred. The fiber diameter of carbon fibers constituting the carbon paper is, for example, 10 ⁇ m to 20 ⁇ m. A commercially available porous material may be used as the porous current collector.
- the thickness of the porous current collector is preferably 0.1 mm to 1 mm, more preferably 0.1 mm to 0.5 mm, still more preferably 0.1 mm to 0.3 mm. If the thickness is within such a range, for example, the reaction region, specifically, the three-phase interface consisting of the ion-conducting phase (LDH), the electronic-conducting phase (porous current collector), and the gas phase (air) can be widened. can be secured.
- the porosity of the porous current collector (substantially the air electrode) is preferably 60% to 95%. When the porous current collector is carbon paper, the porosity is more preferably 60% to 90%.
- porosity is within such a range, for example, excellent gas diffusibility can be secured and a wide reaction region can be secured. In addition, since the pores (voids) are increased, clogging due to generated water is less likely to occur. Porosity can be measured by a mercury intrusion method.
- the air electrode is produced, for example, by depositing the LDH on a porous current collector. Specifically, the production of LDH can be carried out in the presence of a porous current collector.
- the particulate LDH for example, plate-like fine particles
- the particulate LDH is bonded and/or adhered (bonded, etc.) to the surface of the porous current collector 12a to form the catalyst layer 12b.
- the catalyst layer 12b may contain a second LDH having a composition different from that of the LDH.
- the LDH constituting the catalyst layer 12b may have a single composition, or may be a mixture of two or more LDHs having different compositions.
- LDH typically has the form of plate-like particles, and may be bound to the entire porous current collector (as a result, may cover the entire porous current collector). ), may be bonded to a part of the porous current collector (as a result, may cover a part of the porous current collector).
- the LDHs (plate-like particles) are bonded such that their main surfaces are perpendicular or oblique to the surface of the porous current collector.
- the LDHs are linked to each other. With such a configuration, the reaction resistance can be reduced.
- LDH can function not only as a catalyst (air electrode catalyst) but also as a hydroxide ion conducting material.
- the sizes of LDHs (plate-like particles) of each composition are typically different from each other.
- the LDHs (plate-like particles) having the larger size are bonded such that their main surfaces are perpendicular or oblique to the surface of the porous current collector 12a. .
- the diffusion of oxygen to the porous current collector 12a can be promoted, and the amount of oxygen supported on the porous current collector 12a can be increased.
- the air electrode may further contain an air electrode catalyst other than LDH and/or a hydroxide ion conductive material.
- an air electrode catalyst other than LDH and/or a hydroxide ion conductive material.
- cathode catalysts and/or hydroxide ion conducting materials other than LDH include metal oxides, metal nanoparticles, carbon materials, and combinations thereof.
- the air electrode may further include a material capable of adjusting the moisture content.
- LDH can serve as such material.
- Other examples of materials with adjustable moisture content include zeolites, calcium hydroxide, and combinations thereof.
- the air electrode 12 may be composed of a single layer including a porous current collector 12a and a catalyst layer 12b covering the surface of the porous current collector 12a as shown in FIG.
- the structure is different from the outer layer on the side (inner side) where the separator 16 is arranged.
- An inner layer may be formed.
- the internal layer is, for example, a mixture containing a hydroxide ion conductive material, a conductive material, an air electrode catalyst, and an organic polymer in a predetermined portion (end in the thickness direction) inside the porous current collector. Filled and formed.
- LDH is preferred. LDH is not limited to the LDH according to the embodiment of the present invention described in section A above, and any appropriate LDH can be used. LDH can be typically represented by the following general formula (II). (M 2+ ) 1-Y (M 3+ ) Y (OH) 2 (A n- ) Y/n ⁇ mH 2 O (II) In formula (II), M 2+ is at least one divalent cation, M 3+ is at least one trivalent cation, A n- is an n-valent anion, and n is 1 or more.
- M 2+ include Ni 2+ , Mg 2+ , Ca 2+ , Mn 2+ , Fe 2+ , Co 2+ , Cu 2+ and Zn 2+ .
- M 3+ include Fe 3+ , Al 3+ , Co 3+ , Cr 3+ , In 3+ and V 3+ .
- LDHs include Mg--Al-based LDHs and transition metal-containing LDHs (eg, Ni--Fe-based LDHs, Co--Fe-based LDHs, and Ni--Fe--V-based LDHs).
- the hydroxide ion conducting material may be the same material as the cathode catalyst.
- Conductive materials include, for example, conductive ceramics, carbon materials, and combinations thereof.
- Specific examples of conductive ceramics include LaNiO 3 and LaSr 3 Fe 3 O 10 .
- Specific examples of carbon materials include carbon black, graphite, carbon nanotubes, graphene, reduced graphene oxide, and combinations thereof.
- the conductive material may also be the same material as the cathode catalyst.
- Cathode catalysts include LDH and other metal hydroxides, metal oxides, metal nanoparticles, carbon materials, nitrides, and combinations thereof. Preferred are LDH, metal oxides, metal nanoparticles, carbon materials, and combinations thereof. LDH is as described above for the hydroxide ion conductive material.
- Specific examples of metal hydroxides include Ni--Fe--OH, Ni--Co--OH, and combinations thereof. These may further contain a third metal element.
- Specific examples of metal oxides include Co3O4 , LaNiO3 , LaSr3Fe3O10 , and combinations thereof.
- Metal nanoparticles are typically metal particles with a particle size of 2 nm to 30 nm.
- metal nanoparticles include Pt and Ni—Fe alloys.
- carbon materials include carbon black, graphite, carbon nanotubes, graphene, reduced graphene oxide, and combinations thereof, as described above.
- the carbon material may further contain metallic elements and/or other elements such as nitrogen, boron, phosphorus, sulfur, and the like. With such a configuration, the catalytic performance of the carbon material can be improved.
- Nitrides include, for example, TiN.
- binder resin can be used as the organic polymer.
- organic polymers include butyral-based resins, vinyl alcohol-based resins, celluloses, and vinyl acetal-based resins.
- a butyral resin is preferred.
- the air electrode 12 may be provided in advance as a laminate with the separator 16 .
- a hydroxide ion conductive dense separator is used as the separator.
- the hydroxide ion conductive dense separator the electrolytic solution is isolated from the air electrode, and evaporation of water contained in the electrolytic solution can be suppressed.
- an LDH separator can be used as the hydroxide ion conducting dense separator. LDH separators are typically used in metal-air secondary batteries, and such metal-air secondary batteries have an excellent ability to prevent both positive and negative electrode short circuits and carbon dioxide contamination due to metal dendrites. There are advantages. Moreover, there is also the advantage that the denseness of the LDH separator can satisfactorily suppress the evaporation of water contained in the electrolytic solution.
- the LDH separator prevents the penetration of the electrolyte into the air electrode, the electrolyte does not exist in the air electrode.
- a general separator For example, compared to a metal-air secondary battery using a porous polymer separator, the hydroxide ion conductivity tends to be lower, and the charge/discharge performance tends to be lower.
- LDH separators are similarly applicable to hydroxide ion conducting dense separators other than LDH separators, as long as they do not impair technical consistency. That is, in the following description, the LDH separator can be read as a hydroxide ion conducting dense separator as long as it does not impair technical consistency.
- LDH separator Any appropriate configuration can be adopted as the LDH separator.
- the LDH separator the configurations described in WO 2013/073292, WO 2016/076047, WO 2016/067884, WO 2015/146671, and WO 2018/163353 are used. can be adopted. The descriptions of these publications are incorporated herein by reference.
- the LDH separator may include a porous substrate and a layered double hydroxide (LDH) and/or LDH-like compound.
- LDH separator refers to a separator containing LDH and/or LDH-like compounds (LDH and LDH-like compounds can be collectively referred to as a hydroxide ion-conducting layered compound), It is defined as selectively passing hydroxide ions by utilizing the hydroxide ion conductivity of the conductive layered compound.
- LDH-like compound is a hydroxide and/or oxide having a layered crystal structure similar to LDH, although it may not be strictly called LDH, and can be said to be an equivalent of LDH. is. However, as a broad definition, "LDH” can be interpreted as including not only LDH but also LDH-like compounds.
- the LDH-like compound preferably contains Mg and Ti, and optionally Y and/or Al.
- an LDH-like compound which is a hydroxide and/or oxide of a layered crystal structure containing at least Mg and Ti, as a hydroxide ion conductive material instead of conventional LDH, alkali resistance can be improved. It is possible to provide a hydroxide ion conductive separator that is excellent and capable of more effectively suppressing short circuits caused by zinc dendrites.
- preferred LDH-like compounds are hydroxides and/or oxides having a layered crystal structure containing Mg and Ti and optionally Y and/or Al, and more preferred LDH-like compounds are Mg, Ti , Y and Al with a layered crystal structure.
- the above elements may be replaced with other elements or ions to the extent that the basic properties of the LDH-like compound are not impaired.
- the LDH-like compound is preferably Ni-free.
- LDH-like compounds can be identified by X-ray diffraction methods. Specifically, the LDH separator is typically in the range of 5° ⁇ 2 ⁇ ⁇ 10°, more typically 7° ⁇ 2 ⁇ ⁇ 10°, when measured by an X-ray diffraction method for the surface of the LDH separator. A peak derived from the LDH-like compound is detected in the range of .
- LDH is a material with a layer-by-layer structure in which exchangeable anions and H 2 O are present as intermediate layers between stacked hydroxide layers.
- the interlayer distance of the layered crystal structure can be determined by Bragg's equation using 2 ⁇ corresponding to the peak derived from the LDH-like compound in the X-ray diffraction pattern.
- the interlayer distance of the layered crystal structure constituting the LDH-like compound thus determined is typically 0.883 nm to 1.8 nm, more typically 0.883 nm to 1.3 nm.
- the atomic ratio of Mg/(Mg+Ti+Y+Al) in the LDH-like compound, determined by energy dispersive X-ray spectroscopy (EDS), is preferably 0.03-0.25, more preferably 0.05-0. 2.
- the atomic ratio of Ti/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0.40 to 0.97, more preferably 0.47 to 0.94.
- the atomic ratio of Y/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0 to 0.45, more preferably 0 to 0.37.
- the atomic ratio of Al/(Mg+Ti+Y+Al) in the LDH-like compound is preferably 0 to 0.05, more preferably 0 to 0.03. Within the above range, the alkali resistance is even more excellent, and the effect of suppressing short circuits caused by zinc dendrites (that is, dendrite resistance) can be more effectively realized.
- LDH conventionally known as an LDH separator can be represented by the above formula (II).
- the atomic ratios in LDH-like compounds generally deviate from the general formula for LDH. Therefore, it can be said that an LDH-like compound generally has a composition ratio (atomic ratio) different from conventional LDH.
- an energy dispersive X-ray spectrometer eg, X-act, manufactured by Oxford Instruments
- An image is taken at an acceleration voltage of 20 kV and a magnification of 5,000.
- 3-point analysis is performed in the point analysis mode with an interval of about 5 ⁇ m, 3) the above 1) and 2) are repeated once, and 4) the average value of a total of 6 points is calculated. is preferred.
- the separator (LDH separator) 16 preferably includes a porous substrate (polymeric porous substrate) 16a made of a polymeric material and a porous substrate that closes the pores of the porous substrate, as conceptually shown in FIG. and LDH16b. Substantially, the pores of the porous substrate 16a do not have to be completely closed, and residual pores P may exist slightly. By including the polymer porous substrate, it can be bent even when pressurized and does not crack easily. Can be pressurized. Such pressurization is particularly advantageous when a laminated battery is constructed by alternately incorporating a plurality of air electrode/separator laminates together with a plurality of metal negative electrodes into a battery container.
- a battery module is constructed by housing a plurality of stacked batteries in one module container.
- pressurizing a metal-air secondary battery minimizes (preferably eliminates) the gap that allows metal dendrite growth between the negative electrode and the LDH separator, thereby more effectively preventing metal dendrite growth. can be expected.
- by closing the pores of the polymeric porous substrate with LDH to make it highly dense it is possible to provide an LDH separator that can more effectively suppress short circuits caused by metal dendrites.
- the region of the LDH 16b is drawn so as not to be connected between the upper surface and the lower surface of the LDH separator 16, but this is because the cross section is drawn two-dimensionally, and the actual LDH separator , the region of the LDH 16b is connected between the upper surface and the lower surface, whereby the hydroxide ion conductivity of the LDH separator 16 is ensured.
- the porous polymer substrate has the following properties: 1) flexibility (and therefore, it is difficult to break even if it is made thin); 4) It is easy to manufacture and handle.
- the LDH separator containing the polymeric porous substrate can be easily folded or sealed by 5) by making use of the advantage derived from the flexibility of the above 1).
- Specific examples of polymeric materials include polystyrene, polyether sulfone, polyolefin (eg, polyethylene, polypropylene), epoxy resin, polyphenylene sulfide, fluororesin (tetrafluorinated resin: PTFE, etc.), cellulose, nylon, and their A combination is included.
- Polystyrene, polyether sulfone, polyolefin (e.g., polyethylene, polypropylene), epoxy resin, polyphenylene sulfide, fluororesin (tetrafluorinated resin: PTFE, etc.), nylon are preferable from the viewpoint of thermoplastic resins suitable for hot pressing. , and combinations thereof. All of these materials have alkali resistance as resistance to electrolytic solutions. More preferred polymeric materials are polyolefins such as polypropylene and polyethylene, and particularly preferred are polypropylene and polyethylene, since they are excellent in hot water resistance, acid resistance and alkali resistance and are low in cost.
- LDH is incorporated throughout the thickness of the porous substrate (for example, most or almost all of the pores inside the porous substrate are filled with LDH. is particularly preferred.
- a commercially available microporous polymer membrane can be used as such a porous polymer substrate.
- the hardness, brittleness, etc. of LDH which is a ceramic material, are offset or reduced by the flexibility, toughness, etc. It is possible to realize the above-described excellent resistance to pressure and workability and assembling property while maintaining the above characteristics.
- LDH 16b Any suitable LDH can be used as the LDH 16b as long as it can close the pores of the porous polymer substrate and densify the LDH separator.
- LDH the LDH according to the embodiment of the present invention may be used, or any LDH other than the embodiment of the present invention may be used.
- LDH according to embodiments of the present invention is as described in section A above.
- the LDH described in the above section C-1 may be used, or the LDH described in the above international publication incorporated herein may be used.
- the LDH separator 16 preferably has as few residual pores P (pores not blocked by LDH) as possible.
- the average porosity due to the residual pores P of the LDH separator is, for example, 0.03% or more and less than 1.0%, preferably 0.05% to 0.95%, more preferably 0.05% to 0.9%, more preferably 0.05% to 0.8%, and particularly preferably 0.05% to 0.5%. If the average porosity is in such a range, the pores of the porous substrate 16a are sufficiently closed with the LDH 16b, and extremely high density can be achieved, and as a result, the short circuit caused by metal dendrites is further effectively prevented. can be effectively suppressed.
- the LDH separator 16 can exhibit sufficient functions as a hydroxide ion-conducting dense separator.
- the average porosity was determined by a) cross-sectional polishing of the LDH separator with a cross-section polisher (CP), b) cross-sectional images of the functional layer at a magnification of 50,000 times with a FE-SEM (field emission scanning electron microscope) in two fields. c) Based on the acquired image data of the cross-sectional image, image inspection software (e.g., HDDevelop, manufactured by MVTecSoftware) is used to calculate the porosity of each of the two fields of view, and to obtain the average value of the obtained porosities. can be obtained by image inspection software (e.g., HDDevelop, manufactured by MVTecSoftware) is used to calculate the porosity of each of the two fields of view, and to obtain the average value of the obtained porosities. can be obtained by
- the LDH separator 16 is typically gas impermeable and/or water impermeable. In other words, the LDH separator 16 is densified to be gas impermeable and/or water impermeable.
- the term “having gas impermeability” means that even if helium gas is brought into contact with one side of the object to be measured in water at a differential pressure of 0.5 atm, bubbles due to helium gas are generated from the other side. means that you cannot see
- the term “having water impermeability” means that water coming into contact with one side of the object to be measured does not permeate to the other side.
- the LDH separator 16 selectively passes only hydroxide ions due to its hydroxide ion conductivity, and can exhibit its function as a battery separator. Furthermore, the structure is extremely effective in preventing short circuits between the positive and negative electrodes by physically preventing penetration of the separator by metal dendrites generated during charging. Since the LDH separator has hydroxide ion conductivity, it is possible to efficiently transfer necessary hydroxide ions between the positive electrode and the negative electrode to realize charge-discharge reactions in the positive electrode and the negative electrode.
- the LDH separator 16 preferably has a He permeability per unit area of 3.0 cm/min-atm or less, more preferably 2.0 cm/min-atm or less, and still more preferably 1.0 cm/min-atm. It is below.
- the He permeation rate is within such a range, it is possible to extremely effectively suppress permeation of metal ions in the electrolytic solution. As a result, it is theoretically considered that the growth of metal dendrites can be effectively suppressed when used in a metal-air secondary battery.
- the He permeation rate is determined by a process of supplying He gas to one side of the separator to allow the He gas to permeate through the separator, and a process of calculating the He permeation rate and evaluating the compactness of the hydroxide ion conducting dense separator. measured via.
- the degree of He permeation is determined by the formula F/(P ⁇ S) using the permeation amount F of He gas per unit time, the differential pressure P applied to the separator when the He gas permeates, and the membrane area S through which the He gas permeates. Calculated.
- the thickness of the separator 16 is, for example, 5 ⁇ m to 200 ⁇ m.
- the obtained metal-air secondary battery can (i) prevent both positive and negative electrode short circuits and carbon dioxide contamination due to metal dendrites. , (ii) that the evaporation of water contained in the electrolytic solution can be suppressed, and (iii) that it has excellent charge/discharge performance.
- Example 1 An aqueous medium containing 45% by weight of ultrapure water and 55% by weight of ethanol was prepared. 8.34 mmol of NiCl2 , 2.98 mmol of FeCl3, 2.98 mmol of VCl3 , 0.31 mmol of CoCl2 and 4.21 mmol of Mn(NO3)2 were dissolved in this aqueous medium and stirred for 10 minutes. to prepare a solution. Acetylacetone was added to this solution. The amount of acetylacetone added was 0.017% (molar ratio) with respect to the total amount of Ni, Fe, V, Co and Mn elements. The solution was stirred for 30 minutes and then propylene oxide was added.
- the amount of propylene oxide added was 0.24% (molar ratio) with respect to the total amount of Ni, Fe, V, Co and Mn elements.
- the solution was stirred for 1 minute and then allowed to stand for 3 hours. As a result, the solution gelled spontaneously. When the resulting gel was allowed to stand for another 24 hours, it spontaneously formed into a sol. A series of operations were performed at room temperature.
- the obtained sol was separated by centrifugation, and the obtained particles were washed with water and then with ethanol in this order (chlorides, nitrates, reaction by-products, etc. were removed). After that, the particles were dried at room temperature and pulverized in a mortar to obtain a sample powder.
- Examples 2 to 10 Experimental Example 1 and Comparative Examples 1 to 3> A sample powder was obtained in the same manner as in Example 1 except that the composition ratio shown in Table 1 was used.
- Example 2-1 to 2-4 A sample powder was obtained in the same manner as in Example 1 except that the composition ratio shown in Table 2 was used.
- Example 3-1 to 3-2> A sample powder was obtained in the same manner as in Example 1 except that the composition ratio shown in Table 3 was used.
- Example 1 The obtained samples were subjected to the following measurements.
- the X-ray diffraction pattern of Example 1 is shown in FIG. 4A, and the SEM image and elemental map image of Example 1 are shown in FIG. 4B.
- X-Ray Diffraction Measurement An X-ray diffraction pattern was obtained for the obtained sample using RINT-TTRIII manufactured by Rigaku Corporation. The measurement conditions are as follows. ⁇ X-ray source: Cu-K ⁇ ray ⁇ Output: 50 kV, 300 mA ⁇ Step angle: 0.020° ⁇ Scanning speed: 2.00°/min ⁇ Diffraction angle 2 ⁇ : 5° to 70° 2.
- SEM-EDX Measurement The obtained sample was subjected to elemental mapping by energy dispersive X-ray spectroscopy (SEM-EDX) using a scanning electron microscope (SEM). Specifically, a scanning transmission electron microscope (SU3500 manufactured by Hitachi High-Technologies Co., Ltd.) and an energy dispersive X-ray analyzer attached thereto (manufactured by HORIBA, Ltd., detector: X-MAX20, analysis Using an apparatus: EX-370), 1) capture an image at an acceleration voltage of 10 kV and a magnification of 20,000 times, 2) perform a three-point analysis with an interval of about 5 ⁇ m in the point analysis mode, and 3) the above 1) and 2) was repeated once more, and 4) the composition analysis was performed by calculating the average value of a total of 6 points.
- SEM scanning transmission electron microscope
- the peaks derived from LDH are observed in the X-ray diffraction pattern of Example 1, so that LDH was obtained in Example 1. I can say. In the X-ray diffraction patterns of other Examples, Comparative Examples, and Experimental Examples, peaks derived from LDH were similarly observed.
- FIG. 4B in the element map image of Example 1, the mapping shapes of Ni, Fe, V, Co and Mn are substantially the same, and these elements are present at almost the same position. It can be said that the elements are not simply mixed but compounded. Moreover, it was confirmed that the result of the composition analysis corresponds to the charge ratio of the raw material (salt). The same results as in Example 1 were obtained from elemental map images of other Examples, Comparative Examples, and Experimental Examples.
- the resulting sample was evaluated for its performance as a catalyst for OER using a Rotating Ring Disk Electrodes (RRDE) measurement method.
- a product name "rotating ring disk electrode device” manufactured by BAS was used as the measuring device.
- a platinum ring-glassy carbon (GC) disk electrode manufactured by BAS was used as an electrode.
- a 0.1 M KOH aqueous solution was used as an electrolytic solution. 5 mg of the obtained sample and 3000 ⁇ L of butanol were ultrasonically mixed for 1 hour to obtain a liquid for measurement.
- FIG. 5 shows a graph comparing the relationship between the potential with respect to the hydrogen electrode and the current density for Example 1, Comparative Examples 1 and 3.
- FIG. 5 shows a graph comparing the relationship between the potential with respect to the hydrogen electrode and the current density for Example 1, Comparative Examples 1 and 3.
- Example quinary system
- Comparative Example 1 ternary system
- Comparative Example 3 binary system
- Example 1 An aqueous medium containing 45% by weight of ultrapure water and 55% by weight of ethanol was prepared. 8.34 mmol of NiCl2 , 2.98 mmol of FeCl3, 2.98 mmol of VCl3 , 0.31 mmol of CoCl2 and 4.21 mmol of Mn(NO3)2 were dissolved in this aqueous medium and stirred for 10 minutes. to prepare a solution. Acetylacetone was added to this solution. The amount of acetylacetone added was 0.017% (molar ratio) with respect to the total amount of Ni, Fe, V, Co and Mn elements. The solution was stirred for 30 minutes and then propylene oxide was added.
- the amount of propylene oxide added was 0.24% (molar ratio) with respect to the total amount of Ni, Fe, V, Co and Mn elements.
- This solution was stirred for 1 minute, and the resulting solution was impregnated into 3 cm x 3 cm carbon paper (manufactured by SGL, product name "Sigracet (registered trademark)"), and then left to stand for 3 hours.
- the solution spontaneously gelled.When the obtained gel was allowed to stand for another 24 hours, it spontaneously formed a sol.A series of operations were performed at room temperature. After washing the surface with ion-exchanged water, it was dried for 3 hours in a dryer at 80° C. Thus, an air electrode was obtained.
- FIG. 1 An evaluation cell as shown in FIG. 1 was produced. Specifically, a metal zinc plate (negative electrode) is placed in a container, and a nonwoven fabric (not shown in FIG. 1) is placed thereon. A 5.4 M KOH aqueous solution (electrolyte) was added to the extent that the concentration did not reach . Next, the separator and the air electrode obtained above were arranged in this order on the nonwoven fabric to obtain an evaluation cell.
- the layered double hydroxide according to the embodiment of the present invention can be suitably used as a catalyst for the air electrode of metal-air secondary batteries.
- metal-air secondary battery 12 air electrode (positive electrode) 12a porous current collector 12b catalyst layer (layered double hydroxide) 14 Metal Negative Electrode 16 Separator 18 Electrolyte
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
Abstract
Description
1つの実施形態においては、上記層状複水酸化物のエネルギー分散型X線分光法(EDS)により決定される、(Ni+Mn)/(Ni+Fe+V+Co+Mn)の原子比は、0.6以上0.8以下である。
1つの実施形態においては、上記層状複水酸化物のエネルギー分散型X線分光法(EDS)により決定される、Mn/Niの原子比は、0.2以上0.8以下である。
1つの実施形態においては、上記層状複水酸化物のエネルギー分散型X線分光法(EDS)により決定される、Mn/(Ni+Fe+V+Co+Mn)の原子比は、0を超えて0.4以下である。
本発明の別の局面によれば、上記層状複水酸化物の製造方法が提供される。この製造方法は、Ni、Fe、V、CoおよびMnの塩を、それぞれ所定のモル比で水性媒体に溶解させた溶液を調製すること、前記溶液の調製時または調製後にアセチルアセトンを添加すること、前記アセチルアセトンを添加した溶液に酸化プロピレンを添加すること、および、前記酸化プロピレンを添加した溶液を所定時間放置すること、を含む。
1つの実施形態においては、上記製造方法は、上記酸化プロピレンを添加した溶液を所定時間放置してゲルを得ること、および、上記ゲルを所定時間放置してゾルを得ること、を含む。
本発明のさらに別の局面によれば、金属空気二次電池が提供される。この金属空気二次電池は、上記空気極と、セパレータと、電解液と、金属負極と、を有する。
1つの実施形態においては、上記セパレータは、水酸化物イオン伝導緻密セパレータであり、上記電解液は、上記セパレータにより上記空気極と隔離されている。
本発明の実施形態による層状複水酸化物(LDH)は、Ni、Fe、VおよびCoの四元素を含む。具体的には、少なくともこれらの四元素が複合化されたLDHであり得る。少なくともNi、Fe、VおよびCoの四元素を含むことにより、優れた触媒機能(例えば、酸素発生触媒機能)を実現することができる。具体的には、金属空気二次電池の空気極の触媒として用いる場合の触媒活性評価において、立ち上がり電位(on-set potential)を低くすることができ、および/または、所定の電流密度における電位を低く(低抵抗に)することができる。これは、例えば、LDHに含まれる元素が多いことによって活性点の数および/または密度が増大し、かつ、そのような活性点同士の相互作用が増大することによると推定され得る。なお、本明細書における効果およびメカニズムに関する推定は本発明を限定するものではなく、かつ、このような推定により本発明を拘束するものではない。
(M2+)1-X(M3+)X(OH)2(An-)X/n・mH2O・・・(I)
式(I)中、M2+は少なくとも一種の2価の陽イオンであり、M3+は少なくとも一種の3価の陽イオンであり、An-はn価の陰イオンであり、nは1以上の整数であり、mは任意の(0を超える)実数である。
仮に、上記LDHの水酸化物層が主としてNi、Fe、V、CoおよびMnで構成されるとした場合、例えば、上記一般式(I)において、M2+は、Ni2+およびMn2+を含み得、M3+は、Fe3+、V3+およびCo3+を含み得る。(Ni+Mn)/(Ni+Fe+V+Co+Mn)の原子比は、好ましくは0.6以上である。一方、(Ni+Mn)/(Ni+Fe+V+Co+Mn)の原子比は、好ましくは0.8以下であり、より好ましくは0.75以下であり、さらに好ましくは0.7以下である。Mn/Niの原子比は、好ましくは0.2以上0.8以下であり、より好ましくは0.25以上0.75以下であり、さらに好ましくは0.3以上0.7以下である。
上記LDHは、任意の適切な方法により製造され得る。1つの実施形態においては、上記LDHは、いわゆるゾル-ゲル法により作製され得る。例えば、上記LDHの製造方法は、Ni、Fe、V、Coおよび必要に応じて上記第五元素(1つの実施形態においては、Mn)の塩を、それぞれ所定のモル比で水性媒体に溶解させた溶液を調製すること;溶液の調製時または調製後に(前記水性媒体または前記溶液に)アセチルアセトンを添加すること;アセチルアセトンを添加した溶液に酸化プロピレンを添加すること;および、酸化プロピレンを添加した溶液を所定時間放置すること;を含む。
図1は、本発明の1つの実施形態による金属空気二次電池の概略の構成を示す模式図である。金属空気二次電池10は、空気極(正極)12と、金属負極14と、空気極12と金属負極14との間に配置されたセパレータ16と、電解液18とを有し、これらは容器20に収容されている。空気極12は、外部の空気と接触可能な状態で容器20に収容されている。
図2は、図1に示す金属空気二次電池の空気極の一部の一例を拡大して示す図である。空気極12は、多孔性集電体12aと、多孔性集電体12aの表面を覆う触媒層12bとを含む。触媒層12bは、上記LDHを含む。
(M2+)1-Y(M3+)Y(OH)2(An-)Y/n・mH2O・・・(II)
式(II)中、M2+は少なくとも一種の2価の陽イオンであり、M3+は少なくとも一種の3価の陽イオンであり、An-はn価の陰イオンであり、nは1以上の整数であり、mは任意の(0を超える)実数であり、Yは0.1~0.4である。M2+としては、例えば、Ni2+、Mg2+、Ca2+、Mn2+、Fe2+、Co2+、Cu2+、Zn2+が挙げられる。M3+としては、例えば、Fe3+、Al3+、Co3+、Cr3+、In3+、V3+が挙げられる。LDHの具体例としては、Mg-Al系LDH、遷移金属を含むLDH(例えば、Ni-Fe系LDH、Co-Fe系LDH、Ni-Fe-V系LDH)が挙げられる。水酸化物イオン伝導材料は空気極触媒と同一材料であってもよい。
上記セパレータとしては、例えば、水酸化物イオン伝導緻密セパレータが用いられる。水酸化物イオン伝導緻密セパレータによれば、電解液は空気極と隔離され、電解液に含まれる水分の蒸発を抑制することができる。水酸化物イオン伝導緻密セパレータとしては、代表的には、LDHセパレータを用いることができる。LDHセパレータは、代表的には金属空気二次電池に用いられるところ、そのような金属空気二次電池には、金属デンドライトによる正負極間の短絡および二酸化炭素の混入の両方を防止できるという優れた利点がある。また、LDHセパレータの緻密性により、電解液に含まれる水分の蒸発を良好に抑制できるという利点もある。一方で、LDHセパレータは空気極への電解液の浸透を阻止するので、空気極には電解液が存在しないこととなり、その結果、空気極への電解液の浸透を許容する一般的なセパレータ(例えば、多孔高分子セパレータ)を用いた金属空気二次電池と比較して、水酸化物イオン伝導性が低くなる傾向があり、充放電性能が低下する傾向にある。本発明の実施形態による空気極とLDHセパレータとの積層体を用いることにより、LDHセパレータの上記優れた利点を維持しつつ、このような不都合を解消することができる。なお、以下の説明においてLDHセパレータに関して言及される内容は、技術的な整合性を損なわないかぎりにおいて、LDHセパレータ以外の水酸化物イオン伝導緻密セパレータにも同様に当てはまるものとする。すなわち、以下の記載において、技術的な整合性を損なわないかぎりにおいて、LDHセパレータは水酸化物イオン伝導緻密セパレータと読み替え可能である。
超純水を45重量%およびエタノールを55重量%含む水性媒体を調製した。この水性媒体に、NiCl2を8.34mmol、FeCl3を2.98mmol、VCl3を2.98mmol、CoCl2を0.31mmolおよびMn(NO3)2を4.21mmol溶解させ、10分間攪拌して、溶液を調製した。この溶液にアセチルアセトンを添加した。アセチルアセトンの添加量は、Ni、Fe、V、CoおよびMn元素の合計量に対して、0.017%(モル比)であった。この溶液を30分間攪拌し、次いで、酸化プロピレンを添加した。酸化プロピレンの添加量は、Ni、Fe、V、CoおよびMn元素の合計量に対して、0.24%(モル比)であった。この溶液を1分間攪拌し、次いで、3時間静置した。その結果、溶液は自発的にゲル化した。得られたゲルをさらに24時間静置したところ、自発的にゾル化した。なお、一連の操作は室温で行った。
表1に示す組成比としたこと以外は実施例1と同様にして、試料粉末を得た。
表2に示す組成比としたこと以外は実施例1と同様にして、試料粉末を得た。
表3に示す組成比としたこと以外は実施例1と同様にして、試料粉末を得た。
1.X線回折測定
得られた試料について、株式会社リガク製のRINT-TTRIIIを用いてX線回折パターンを得た。測定条件は以下のとおりである。
・X線源:Cu-Kα線
・出力:50kV、300mA
・ステップ角:0.020°
・スキャン速度:2.00°/min
・回折角2θ:5°~70°
2.SEM-EDX測定
得られた試料について、走査型電子顕微鏡(SEM)を用いたエネルギー分散型X線分光法(SEM-EDX)により、元素マッピングを行った。具体的には、走査型透過電子顕微鏡(株式会社日立ハイテクノロジーズ製のSU3500)と、それに付属しているエネルギー分散型X線分析装置(株式会社製堀場製作所製、検出器:X-MAX20、分析装置:EX-370)を用いて、1)加速電圧10kV、倍率20,000倍で像を取り込み、2)点分析モードで5μm程度間隔を空け、3点分析を行い、3)上記1)及び2)をさらに1回繰り返し行い、4)合計6点の平均値を算出することにより、組成分析を行った。
図4Bに示すように、実施例1の元素マップ像において、Ni、Fe、V、CoおよびMnのマッピング形状が実質的に同一であり、これらの元素がほぼ同一の位置に存在するので、これらの元素が単に混合されたのではなく複合化されているといえる。また、組成分析の結果は、原料(塩)の仕込み比に対応することが確認された。なお、他の実施例、比較例および実験例の元素マップ像においても、実施例1と同様の結果が得られた。
得られた試料について、回転リングディスク電極(RRDE:Rotating Ring Disk Electrodes)測定法を用いて、OERに対する触媒としての性能を評価した。
具体的には、測定装置としてBAS社製の製品名「回転リングディスク電極装置」を用いた。電極としてBAS社製の白金リング-グラッシーカーボン(GC)ディスク電極を用いた。電解液として0.1MのKOH水溶液を用いた。得られた試料5mgおよびブタノール3000μLを超音波で1時間混合し、測定用液を得た。この測定用液6μLをディスク電極にキャストして乾燥させた後、さらに、0.1重量%のNafion(登録商標、Sigma-Aldrich社製)溶液4μLをディスク電極にキャストし、回転数1600rpm、チラー温度25℃、酸素雰囲気下で対流ボルタンメトリー測定を行い、水素電極に対する電位と電流密度との関係から立ち上がり電位および電流密度10mA/cm2における電位を求めた。なお、立ち上がり電位は、ΔA/ΔVが3となるときの電位とした。
評価結果を表1~3に示す。また、実施例1、比較例1および比較例3について、水素電極に対する電位と電流密度との関係を比較するグラフを図5に示す。
実施例1および比較例3について、以下の手順により、充放電試験を行った。
<実施例1>
超純水を45重量%およびエタノールを55重量%含む水性媒体を調製した。この水性媒体に、NiCl2を8.34mmol、FeCl3を2.98mmol、VCl3を2.98mmol、CoCl2を0.31mmolおよびMn(NO3)2を4.21mmol溶解させ、10分間攪拌して、溶液を調製した。この溶液にアセチルアセトンを添加した。アセチルアセトンの添加量は、Ni、Fe、V、CoおよびMn元素の合計量に対して、0.017%(モル比)であった。この溶液を30分間攪拌し、次いで、酸化プロピレンを添加した。酸化プロピレンの添加量は、Ni、Fe、V、CoおよびMn元素の合計量に対して、0.24%(モル比)であった。この溶液を1分間攪拌し、得られた溶液を3cm×3cmのカーボンペーパー(SGL社製、製品名「Sigracet(シグラセット)(登録商標)」へ含浸させ、次いで、3時間静置した。その結果、溶液は自発的にゲル化した。得られたゲルをさらに24時間静置したところ、自発的にゾル化した。なお、一連の操作は室温で行った。処理が施されたカーボンペーパーの表面をイオン交換水で洗浄した後、80℃の乾燥機内で3時間乾燥させた。こうして空気極を得た。
表1に示す組成比としたこと以外は実施例1と同様にして、空気極を得た。
図1に示すような評価用セルを作製した。具体的には、容器内に金属亜鉛板(負極)を置き、その上に不織布(図1において図示せず)を配置し、得られる評価用セルにおいてセパレータの下面より高く、かつ、セパレータの上面に達しない程度に5.4MのKOH水溶液(電解液)を加えた。次いで、不織布の上にセパレータおよび上記で得られた空気極をこの順に配置し、評価用セルを得た。
得られた評価用セル(空気極側)に対し、水蒸気飽和(25℃)および酸素ガスフロー(200cc/min)下で、充放電試験を行った。充放電試験には、電気化学測定装置(北斗電工社製、「HZ-Pro S12」)を用いた。充放電電流密度8mA/cm2にて10分間放電した後に、10分間の充電を行った(1サイクル)。この操作を、計3サイクル行った。
2サイクル目の容量0.5mAh時の過電圧は、実施例1においては0.616Vであり、比較例3においては0.762Vであった。実施例1においては、充放電反応がより促進されて、過電圧が減少したと考えられる。
12 空気極(正極)
12a 多孔性集電体
12b 触媒層(層状複水酸化物)
14 金属負極
16 セパレータ
18 電解液
Claims (9)
- Ni、Fe、VおよびCoの四元素を含み、
第五元素としてMnをさらに含む、
層状複水酸化物。 - エネルギー分散型X線分光法(EDS)により決定される、(Ni+Mn)/(Ni+Fe+V+Co+Mn)の原子比が、0.6以上0.8以下である、請求項1に記載の層状複水酸化物。
- エネルギー分散型X線分光法(EDS)により決定される、Mn/Niの原子比が、0.2以上0.8以下である、請求項1または2に記載の層状複水酸化物。
- エネルギー分散型X線分光法(EDS)により決定される、Mn/(Ni+Fe+V+Co+Mn)の原子比が、0を超えて0.4以下である、請求項1から3のいずれかに記載の層状複水酸化物。
- 請求項1から4のいずれかに記載の層状複水酸化物の製造方法であって、
Ni、Fe、V、CoおよびMnの塩を、それぞれ所定のモル比で水性媒体に溶解させた溶液を調製すること、
前記溶液の調製時または調製後にアセチルアセトンを添加すること、
前記アセチルアセトンを添加した溶液に酸化プロピレンを添加すること、および、
前記酸化プロピレンを添加した溶液を所定時間放置すること、
を含む、製造方法。 - 前記酸化プロピレンを添加した溶液を所定時間放置してゲルを得ること、および、前記ゲルを所定時間放置してゾルを得ること、を含む、請求項5に記載の製造方法。
- 多孔性集電体と、
前記多孔性集電体の少なくとも一部を覆い、請求項1から4のいずれかに記載の層状複水酸化物を含む触媒層と、
を有する、空気極。 - 請求項7に記載の空気極と、セパレータと、電解液と、金属負極と、を有する、金属空気二次電池。
- 前記セパレータは、水酸化物イオン伝導緻密セパレータであり、前記電解液は、前記セパレータにより前記空気極と隔離されている、請求項8に記載の金属空気二次電池。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023531396A JPWO2023276281A1 (ja) | 2021-07-02 | 2022-03-04 | |
DE112022003391.6T DE112022003391T5 (de) | 2021-07-02 | 2022-03-04 | Geschichtetes doppelhydroxid, verfahren zur herstellung von geschichtetem doppelhydroxid, luftelektrode und metall-luft sekundärbatterie |
CN202280038775.0A CN117460701A (zh) | 2021-07-02 | 2022-03-04 | 层状双氢氧化物、层状双氢氧化物的制造方法、空气极以及金属空气二次电池 |
US18/520,655 US20240097145A1 (en) | 2021-07-02 | 2023-11-28 | Layered double hydroxide, method for producing layered double hydroxide, air electrode, and metal-air secondary battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021110502 | 2021-07-02 | ||
JP2021-110502 | 2021-07-02 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/520,655 Continuation US20240097145A1 (en) | 2021-07-02 | 2023-11-28 | Layered double hydroxide, method for producing layered double hydroxide, air electrode, and metal-air secondary battery |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023276281A1 true WO2023276281A1 (ja) | 2023-01-05 |
Family
ID=84692263
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/009438 WO2023276281A1 (ja) | 2021-07-02 | 2022-03-04 | 層状複水酸化物、層状複水酸化物の製造方法、空気極および金属空気二次電池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240097145A1 (ja) |
JP (1) | JPWO2023276281A1 (ja) |
CN (1) | CN117460701A (ja) |
DE (1) | DE112022003391T5 (ja) |
WO (1) | WO2023276281A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108862406A (zh) * | 2018-06-27 | 2018-11-23 | 中南大学 | 一种碳酸盐前驱体及其制备方法和应用 |
CN111472020A (zh) * | 2019-06-04 | 2020-07-31 | 中山大学 | 一种水滑石基层状催化剂电催化氧化5-羟甲基糠醛制备2,5呋喃二甲酸的方法 |
WO2020250590A1 (ja) * | 2019-06-10 | 2020-12-17 | パナソニックIpマネジメント株式会社 | 層状複水酸化物、水電解セル用触媒、水電解セル、水電解装置および層状複水酸化物の製造方法 |
WO2021176869A1 (ja) * | 2020-03-02 | 2021-09-10 | 日本碍子株式会社 | 層状複水酸化物およびその製造方法、ならびに、該層状複水酸化物を用いた空気極および金属空気二次電池 |
WO2022014242A1 (ja) * | 2020-07-17 | 2022-01-20 | パナソニックIpマネジメント株式会社 | 水電解セルの電極触媒、水電解セル、及び水電解装置 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2782185B1 (en) | 2011-11-16 | 2016-04-20 | NGK Insulators, Ltd. | Zinc-air secondary battery |
EP3125358B1 (en) | 2014-03-28 | 2019-08-28 | NGK Insulators, Ltd. | Air electrode for metal-air battery |
WO2016067884A1 (ja) | 2014-10-28 | 2016-05-06 | 日本碍子株式会社 | 層状複水酸化物緻密膜の形成方法 |
CN108352580A (zh) | 2014-11-13 | 2018-07-31 | 日本碍子株式会社 | 用于锌二次电池的隔板结构体 |
CN109314212B (zh) | 2016-06-24 | 2022-02-08 | 日本碍子株式会社 | 包含层状双氢氧化物的功能层及复合材料 |
JP6550193B2 (ja) | 2017-03-09 | 2019-07-24 | 日本碍子株式会社 | セパレータ/空気極複合体の製造方法 |
-
2022
- 2022-03-04 CN CN202280038775.0A patent/CN117460701A/zh active Pending
- 2022-03-04 JP JP2023531396A patent/JPWO2023276281A1/ja active Pending
- 2022-03-04 DE DE112022003391.6T patent/DE112022003391T5/de active Pending
- 2022-03-04 WO PCT/JP2022/009438 patent/WO2023276281A1/ja active Application Filing
-
2023
- 2023-11-28 US US18/520,655 patent/US20240097145A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108862406A (zh) * | 2018-06-27 | 2018-11-23 | 中南大学 | 一种碳酸盐前驱体及其制备方法和应用 |
CN111472020A (zh) * | 2019-06-04 | 2020-07-31 | 中山大学 | 一种水滑石基层状催化剂电催化氧化5-羟甲基糠醛制备2,5呋喃二甲酸的方法 |
WO2020250590A1 (ja) * | 2019-06-10 | 2020-12-17 | パナソニックIpマネジメント株式会社 | 層状複水酸化物、水電解セル用触媒、水電解セル、水電解装置および層状複水酸化物の製造方法 |
WO2021176869A1 (ja) * | 2020-03-02 | 2021-09-10 | 日本碍子株式会社 | 層状複水酸化物およびその製造方法、ならびに、該層状複水酸化物を用いた空気極および金属空気二次電池 |
WO2022014242A1 (ja) * | 2020-07-17 | 2022-01-20 | パナソニックIpマネジメント株式会社 | 水電解セルの電極触媒、水電解セル、及び水電解装置 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2023276281A1 (ja) | 2023-01-05 |
DE112022003391T5 (de) | 2024-04-18 |
CN117460701A (zh) | 2024-01-26 |
US20240097145A1 (en) | 2024-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5953575B2 (ja) | 全固体アルカリ燃料電池用電解質膜 | |
Xu et al. | Recent advances in hybrid sodium–air batteries | |
Hegde et al. | Role of defects in low-cost perovskite catalysts toward ORR and OER in lithium–oxygen batteries | |
JP5953576B2 (ja) | 金属−空気二次電池用空気極触媒層 | |
US11936069B2 (en) | Layered double hydroxide and method for production thereof, and air electrode and metal-air secondary battery that use said layered double hydroxide | |
JP6148873B2 (ja) | 亜鉛負極合剤、亜鉛負極及び電池 | |
Sharma et al. | Facile synthesis of N-doped graphene supported porous cobalt molybdenum oxynitride nanodendrites for the oxygen reduction reaction | |
JP2018133325A (ja) | 正極及び二次電池 | |
Wang et al. | Perovskite Sr0. 9Y0. 1CoO3− δ nanorods modified with CoO nanoparticles as a bifunctional catalyst for rechargeable Li–O2 batteries | |
Ercolano et al. | Preparation of Ni@ Pt core@ shell conformal nanofibre oxygen reduction electrocatalysts via microwave-assisted galvanic displacement | |
US11862815B2 (en) | Air electrode/separator assembly and metal-air secondary battery | |
Majee et al. | The Perfect Imperfections in Electrocatalysts | |
US20220052399A1 (en) | Air electrode/separator assembly and metal-air secondary battery | |
JP7228706B2 (ja) | 空気極/セパレータ接合体及び亜鉛空気二次電池 | |
WO2023276281A1 (ja) | 層状複水酸化物、層状複水酸化物の製造方法、空気極および金属空気二次電池 | |
WO2019093441A1 (ja) | 非晶質遷移金属酸化物及びその利用 | |
JP6475143B2 (ja) | リチウム空気二次電池およびその製造方法 | |
WO2022209010A1 (ja) | 空気極/セパレータ接合体及び金属空気二次電池 | |
WO2022208993A1 (ja) | 空気極/セパレータ接合体及び金属空気二次電池 | |
KR102427234B1 (ko) | 격자결함을 함유한 다공성 나노복합체 | |
Chandrappa | Non-precious Metal Electrocatalysts for Rechargeable Metal-air Batteries | |
WO2018150919A1 (ja) | マンガン二次電池 | |
JP2018014259A (ja) | 金属空気電池用電解液 | |
Orantek | Improving Electrochemical and Cyclic Stability Performance of Carbon-Supported and Carbon-Free Bifunctional Air Cathodes | |
Kim | Studies on Electrocatalysts for Oxygen Electrochemistry, Hydrogen Evolution, and Carbon Dioxide Conversion and Their Applications |
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: 22832447 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023531396 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280038775.0 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 112022003391 Country of ref document: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 22832447 Country of ref document: EP Kind code of ref document: A1 |