JPWO2019065285A1 - メリライト型複合酸化物 - Google Patents
メリライト型複合酸化物 Download PDFInfo
- Publication number
- JPWO2019065285A1 JPWO2019065285A1 JP2019544572A JP2019544572A JPWO2019065285A1 JP WO2019065285 A1 JPWO2019065285 A1 JP WO2019065285A1 JP 2019544572 A JP2019544572 A JP 2019544572A JP 2019544572 A JP2019544572 A JP 2019544572A JP WO2019065285 A1 JPWO2019065285 A1 JP WO2019065285A1
- Authority
- JP
- Japan
- Prior art keywords
- melilite
- metal
- composite oxide
- positive electrode
- examples
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910001719 melilite Inorganic materials 0.000 title description 14
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 abstract description 43
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 229910021133 SiyGe1-y Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 239000002243 precursor Substances 0.000 description 15
- 229910052723 transition metal Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 238000007654 immersion Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052732 germanium Inorganic materials 0.000 description 9
- -1 hydroxide ions Chemical class 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 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
- 239000003513 alkali Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002738 chelating agent Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- OLQSNYOQJMTVNH-UHFFFAOYSA-N germanium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Ge+4] OLQSNYOQJMTVNH-UHFFFAOYSA-N 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000004685 neutron diffraction pattern Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002250 neutron powder diffraction Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910002738 Ba0.5Sr0.5Co0.8Fe0.2O3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018921 CoO 3 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
- C01G51/68—Cobaltates containing alkaline earth metals, e.g. SrCoO3 containing rare earth, e.g. La0.3Sr0.7CoO3
-
- 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
- H01M4/90—Selection of catalytic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
- Silicon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
(正極)
充電反応(酸素発生反応):4OH−→O2+2H2O+4e−
・・・(1)
放電反応(酸素還元反応):O2+2H2O+4e−→4OH−
・・・(2)
(負極)
充電反応:ZnO+H2O+2e−→Zn+2OH− ・・・(3)
放電反応:Zn+2OH−→ZnO+H2O+2e− ・・・(4)
本実施の形態に係るメリライト型複合酸化物は、一般式(BazSr1−z)2CoxFe2−2x(SiyGe1−y)1+xO7(式中、0≦x≦1,0≦y≦1,0≦z≦1である。但し、x=1且つy=1の場合、x=1且つy=0の場合、及びx=0且つy=0の場合を除く。)で表される。ここで、Co2+、Fe3+、Si4+及びGe4+の原子数の総和は、Ba及びSrの原子数の総和に対し3/2である。また、Co2+、Fe3+、Si4+及びGe4+の電荷の総和は+10となるように設計する。これにより、メリライト型複合酸化物相を形成することができる。
メリライト型複合酸化物の製造方法としては、特に限定されるものではなく、セラミックス材料の各種製造方法を用いることができる。例えば、錯体重合法や水熱合成法等の液相法、焼結法等の固相法等を用いることができる。このうち、液相法は、低温焼成でも化学的に均一性の高い粒子を得ることができ、その結果として小粒径・高比表面積でより高いORR活性及びOER活性を示す正極触媒を得ることができる。
溶液調製工程は、金属源を、目的生成物中に含まれる金属の化学量論比と同様になるよう純水に添加し溶解し、クエン酸を加えて均一になるよう撹拌し、原料溶液を得る工程である。
ゲル化工程は、原料溶液を加熱濃縮してクエン酸ゲルを製造する工程である。
前駆体調製工程は、クエン酸ゲルに熱処理を施すことよって有機分を分解させることで、粉体の前駆体を得る工程である。
必須の態様ではないが、粉砕工程は、前駆体調製工程で得られた紛体の前駆体を粉砕する工程である。
焼成工程は、前駆体を焼成する工程である。
本実施の形態に係る正極触媒は、上述したメリライト型複合酸化物を備えることを特徴とするものである。
本実施の形態に係る金属空気電池は、上述した正極触媒を備えることを特徴とするものである。そして、このような金属空気電池は、充放電特性が高く、また、耐久性が高い。
(実施例1〜28及び参考例1〜5)
以下に示す方法により、正極触媒としての試料を調製した。原料としては、以下のものを用いた。
Ba源:Ba(CH3COO)2(純度99.9%,和光純薬工業)
Sr源:SrNO3(純度99.5%,和光純薬工業)
Co源:Co(CH3COO)2・4H2O(純度99%,和光純薬工業)
Fe源:Fe(NO3)3・9H2O(純度99.9%,和光純薬工業)
Si源:C8H2O4Si(97%,東京化成工業)
Ge源:GeO2(99.99%,高純度化学研究所)
La源:La(NO3)3・6H2O(99.9%,和光純薬工業)
Ca源:Ca(NO3)2・4H2O(99.9%,和光純薬工業)
ゲル化剤:くえん酸C6H8O7(純度98%,和光純薬工業)
目的生成物が2mmolとなるように、目的生成物の金属イオンの化学両論比と同様の仕込み比で各金属源を純水に溶解し、クエン酸を総カチオン量の3倍モル量加えて均一な溶液となるよう撹拌し混合した。混合した原料溶液を120℃に設定した恒温槽に静置し、加熱濃縮した。流動性を失いゲル状となった過飽和のクエン酸ゲルに450℃で熱処理によって、有機分を分解して粉体の前駆体を得た。このようにして得た前駆体を粉砕し、ボックス炉を用いて大気中1000℃で12時間焼成した。
目的生成物が2mmolとなるように、目的生成物の金属イオンの化学両論比と同様の仕込み比で各金属源を純水に溶解し、クエン酸を総カチオン量の3倍モル量加えて均一な溶液となるよう撹拌し混合した。混合した原料溶液を120℃に設定した恒温槽に静置し、加熱濃縮した。流動性を失いゲル状となった過飽和のクエン酸ゲルに450℃で熱処理を施し、有機分を分解して粉体の前駆体を得た。このようにして得た前駆体を粉砕し、ボックス炉を用いて大気中1000℃で12時間焼成した。
実施例5の試料0.15gを、4Mに調整したKOH水溶液5mLに浸漬し、室温(25℃)、40℃又は60℃でそれぞれ24時間静置した。静置後の水溶液の色を目視で確認した。図3は、実施例5の試料のKOH水溶液浸漬前後の水溶液の写真である。
対流ボルタンメトリー(Rotating Disk Electrode,RDE) 法により、実施例1〜28及び参考例1〜5の試料のORR活性及びOER活性の評価を行った。回転電極装置(RRDE−3A,BAS製)の作用電極を1600rpmで回転させ、ポテンショスタット(HZ−7000,北斗電工製又はVersaSTAT4,METEK製)と接続し、電解液に4MのKOH水溶液を用い、サイクリックボルタンメトリー(CV)測定を行った。電極としては、以下のものを使用した。
作用電極(WE):5mmφガラス状カーボン(グラッシーカーボン,GC)電極
対電極(CE):コイル状白金(Pt)電極
参照電極(RE):アルカリ用参照電極(Hg/HgO/4M KOH)
カーボンの前処理として、アセチレンブラック(Acetylene carbon black,99.99%,STREM CHEMICALS)を硝酸中で30分間超音波分散させた後、80℃で一晩加熱撹拌子し、ろ過乾燥後、粉砕した。
5%ナフィオン(商標登録)分散液(和光純薬工業)を水酸化ナトリウム・エタノール(EtOH)溶液で中和し、得られた中和液とエタノールを3:47の体積比で混合してインク用溶媒とした。
サンプル瓶にインク用溶媒:アセチレンブラック:触媒(酸化物試料)=5mL:10mg:50mgの比で入れ、超音波分散させた。
超純水とEtOHで洗浄したグラッシーカーボンにインクを20μL滴下し(触媒量:0.2mg)、完全に乾燥させた。
サイクリックボルタンメトリー測定は以下の手順に従って、適時アルゴンまたは酸素ガスフローを行った後に開始した。測定条件は以下の通りである。
(1)クリーニング(cleaning)測定(in Ar)
0.176V〜−0.324V vs.Hg/HgO,50mV/s,
30cycles
(2)バックグラウンド(BG)測定(in Ar)
0.176V〜−0.324V vs Hg/HgO,1mV/s,
3cycles
(3)O2バブリング
(4)ORR測定(in O2)
0.176V〜−0.324V vs Hg/HgO,1mV/s,
3cycles
(5)OER測定
0.176V〜0.776V vs Hg/HgO,1mV/s,
3cycles
参考例1、実施例7及び実施例9のメリライト型複合酸化物中において、各遷移金属元素が、2aサイト及び4eサイトのいずれのサイトに配置されるのかを調べるため、粉末中性子回折法により、回折パターンを得た後、その回折パターンをRietveld解析により、構造パラメータを精密化して結晶構造の詳細な解析を行った。測定は、大強度陽子加速器施設(J−PARC) 物質・生命科学実験施設(MLF)の飛行時間法粉末中性子回折計 SPICA(BL09)を用いて行った(M.Yonemura,K.Mori,T.Kamiyama et al.,Development of SPICA,New Dedicated Neutron Powder Diffractometer for Battery Studies,J.Phys.Conf.Ser.502,012053,(2014).を参照)。また、解析プログラムとしては、Z−rietveldを用いた(R.Oishi,M.Yonemura,Y.Nishimaki et al.,Rietveld analysis software for J−PARC,Nucl.Instrum.Methods Phys.Res.,Sect.A 600,94,(2009).を参照)。
2 負極
3 電解質
10 金属空気電極
Claims (5)
- 一般式(BazSr1−z)2CoxFe2−2x(SiyGe1−y)1+xO7(式中、0≦x≦1,0≦y≦1,0≦z≦1である。但し、x=1且つy=1且つz=0の場合、x=1且つy=1且つz=1の場合、x=1且つy=0且つz=0の場合、x=1且つy=0且つz=1の場合、x=0且つy=0且つz=0の場合及びx=0且つy=0且つz=1の場合を除く。)で表される
メリライト型複合酸化物。 - 前記一般式中、0.5≦x≦0.9である
請求項1に記載のメリライト型複合酸化物。 - 前記一般式中、0≦y≦0.1である
請求項1又は2に記載のメリライト型複合酸化物。 - 一般式(Baz1Sr1−z1―z2REz2)2Cox1Znx2Fe2−2(x1+x2)(SiyGe1−y)1+x1+x2O7(式中、0≦x1≦1,0≦x2≦0.2,0≦y≦1,0≦z1≦1,0≦z2≦0.2であり、且つx2及びz2の少なくともいずれかが0超である)で表される
メリライト型複合酸化物。 - 前記メリライト型複合酸化物は、前記一般式中、REがYである
請求項4に記載のメリライト型複合酸化物。
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