JP5191166B2 - Material for anode of solid oxide fuel cell - Google Patents
Material for anode of solid oxide fuel cell Download PDFInfo
- Publication number
- JP5191166B2 JP5191166B2 JP2007138884A JP2007138884A JP5191166B2 JP 5191166 B2 JP5191166 B2 JP 5191166B2 JP 2007138884 A JP2007138884 A JP 2007138884A JP 2007138884 A JP2007138884 A JP 2007138884A JP 5191166 B2 JP5191166 B2 JP 5191166B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- fuel cell
- oxide
- fuel
- solid oxide
- 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.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims description 69
- 239000000463 material Substances 0.000 title claims description 34
- 239000007787 solid Substances 0.000 title claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000007772 electrode material Substances 0.000 claims description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 229910018279 LaSrMnO Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 24
- -1 oxygen ion Chemical class 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 16
- 239000003513 alkali Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000010248 power generation Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000011195 cermet Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002737 fuel gas Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 1
- 229910000346 scandium sulfate Inorganic materials 0.000 description 1
- DBTMQFKUVICLQN-UHFFFAOYSA-K scandium(3+);triacetate Chemical compound [Sc+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBTMQFKUVICLQN-UHFFFAOYSA-K 0.000 description 1
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 1
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、固体酸化物型燃料電池の燃料極用材料及びその製造方法に関する。より詳しくは、固体酸化物形燃料電池（以下、ＳＯＦＣ）の燃料電極（以下、アノード）材料として用いられる酸化ニッケル粉末と安定化ジルコニア粉末との混合粉末及びその製造方法ならびにこれを用いたＳＯＦＣに関する。 The present invention relates to a fuel electrode material for a solid oxide fuel cell and a method for producing the same. More specifically, the present invention relates to a mixed powder of nickel oxide powder and stabilized zirconia powder used as a fuel electrode (hereinafter referred to as anode) material of a solid oxide fuel cell (hereinafter referred to as SOFC), a manufacturing method thereof, and an SOFC using the same. .
ＳＯＦＣは、電解質として酸素イオン導電性を有する固体電解質を用いた燃料電池の一つである。ＳＯＦＣの基本的な構造は、燃料極、固体電解質、空気極で構成され、この組み合わせ単位が単セルとなる。通常、この単セルを複数枚積層させ、発電装置として用いられる。 SOFC is one of fuel cells using a solid electrolyte having oxygen ion conductivity as an electrolyte. The basic structure of SOFC is composed of a fuel electrode, a solid electrolyte, and an air electrode, and this combined unit is a single cell. Usually, a plurality of the single cells are stacked and used as a power generator.
一般に、ＳＯＦＣの燃料電極用材料としては、ＮｉＯとＳｃ２Ｏ３安定化ＺｒＯ２（ＳｃＳＺ）又はＹ２Ｏ３安定化ＺｒＯ２（ＹＳＺ）の２成分系で構成されている。ここに、ＮｉＯは、ＳＯＦＣの運転中に還元されてＮｉとなり、Ｎｉ／ＳｃＳＺサーメット又はＮｉ／ＹＳＺサーメットとなる。 In general, the fuel electrode material of SOFC is composed of a two-component system of NiO and Sc 2 O 3 stabilized ZrO 2 (ScSZ) or Y 2 O 3 stabilized ZrO 2 (YSZ). Here, NiO is reduced during operation of the SOFC to Ni, and becomes Ni / ScSZ cermet or Ni / YSZ cermet.
このようなＮｉ／ＳｃＳＺサーメット又はＮｉ／ＹＳＺサーメット用の原料粉末の一般的な製造方法としては、平均粒子径の異なるＮｉＯ粉とＳｃＳＺ粉又はＹＳＺ粉をボールミルのような機械混合法にて固体の状態で混合し、その後に昇温（仮焼）して若干焼結することにより複合化する方法（固体混合法）が知られている（例えば、特許文献１など参照）。
しかしながら、ボールミルのような機械混合法では、平均粒子径の異なる粉体を混合する時、その比重差により粒径の大きな成分が沈降して、粉末の混合ムラが起こりやすく、均一な粉体を得ることは困難である。さらに、ＳＯＦＣの燃料極に適していると考えられている数μｍ以下の粉体を混合する場合には、ＮｉＯ粉あるいはＳｃＳＺ粉又はＹＳＺ粉自体の凝集を一次粒子レベルに解砕することは困難であり、均一な混合粉体を得ることは非常に難しい。 However, in a mechanical mixing method such as a ball mill, when powders having different average particle sizes are mixed, a component having a large particle size settles due to the difference in specific gravity, and powder mixing unevenness easily occurs. It is difficult to get. Furthermore, when powders of several μm or less, which are considered suitable for SOFC fuel electrodes, are mixed, it is difficult to break up the aggregation of NiO powder, ScSZ powder, or YSZ powder itself to the primary particle level. It is very difficult to obtain a uniform mixed powder.
ＳＯＦＣのアノードは、Ｎｉ／ＳｃＳＺサーメットやＮｉ／ＹＳＺサーメットで構成されているが、ＮｉとＳｃＳＺ又はＹＳＺが交錯した構造を有し、Ｎｉが網目状につながり（以下、Ｎｉネットワーク）、電子の導電経路が形成されている。ところが、ＳｃＳＺ又はＹＳＺが均一に分散されていな場合は次のような問題が起こる。すなわち、ＳＯＦＣの発電温度は７００〜１０００℃と高温であるため、Ｎｉが凝集することにより導電経路が切断され、導電経路が減り、それに伴って導電率が下がり、結果として発電効率の低下が起こる。これに対し、ＳｃＳＺ又はＹＳＺがＮｉネットワークの間に均一に分散することができれば、Ｎｉの凝集を効果的に防止することができる。このような見地より、アノード中のＮｉとＳｃＳＺ又はＹＳＺはＮｉネットワークを形成しつつ、ＳｃＳＺ又はＹＳＺがＮｉネットワーク中に均一分散させることが必要である。 The anode of SOFC is composed of Ni / ScSZ cermet or Ni / YSZ cermet, but it has a structure in which Ni and ScSZ or YSZ are interlaced, and Ni is connected in a network shape (hereinafter referred to as Ni network), and conducts electrons. A path is formed. However, when ScSZ or YSZ is not uniformly dispersed, the following problem occurs. That is, since the power generation temperature of SOFC is as high as 700 to 1000 ° C., Ni agglomerates cuts the conductive path, reduces the conductive path, and accordingly decreases the conductivity, resulting in a decrease in power generation efficiency. . On the other hand, if ScSZ or YSZ can be uniformly dispersed between Ni networks, Ni aggregation can be effectively prevented. From this point of view, it is necessary that Ni in the anode and ScSZ or YSZ form a Ni network, while ScSZ or YSZ is uniformly dispersed in the Ni network.
他方、ＳＯＦＣのアノードでは、一定以上の多孔性を有する必要がある。これは、アノード側にある燃料ガスがアノードの中を通り、電解質界面まで燃料ガスを供給することで発電が実現されるためである。このため、燃料ガスを効率良くアノードを通過させて電解質界面まで到達させるためには、前述のＮｉネットワークが多孔性を有しなければならない。ところが、Ｎｉネットワークは、多孔性が大きくなると、当然ながら導電経路が減り、導電率が下がる。 On the other hand, the anode of SOFC needs to have a certain degree of porosity. This is because power generation is realized by the fuel gas on the anode side passing through the anode and supplying the fuel gas to the electrolyte interface. For this reason, in order for fuel gas to efficiently pass through the anode and reach the electrolyte interface, the aforementioned Ni network must be porous. However, when the porosity of the Ni network increases, naturally, the conductive path decreases and the conductivity decreases.
これらＮｉネットワーク中でのＮｉとＳｃＳＺ又はＹＳＺとの均一分散と、Ｎｉネットワークが多孔性を有し、かつ、十分なＮｉでの導電経路を確保するため、それを形成するＮｉＯ粉とＳｃＳＺ粉又はＹＳＺ粉の原料調製時に異なる平均粒子径のものを混ぜたり、また混合粉体合成時に多孔性を高めるための有機物混入等が試みられているが、電極材料として導電性等の点においてさらなる改善の余地がある。 In order to ensure uniform distribution of Ni and ScSZ or YSZ in these Ni networks, and the Ni network is porous, and to secure a sufficient conductive path in Ni, NiO powder and ScSZ powder or Attempts have been made to mix YSZ powders with different average particle sizes, or to mix organic substances to increase porosity during mixed powder synthesis. There is room.
従って、本発明の主な目的は、固体酸化物型燃料電池の燃料極用材料としてより優れた導電性等を発揮できる材料を提供することにある。 Accordingly, a main object of the present invention is to provide a material that can exhibit better conductivity and the like as a material for a fuel electrode of a solid oxide fuel cell.
本発明者は、上記の従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定のプロセスから得られる粉末材料が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventor has found that a powder material obtained from a specific process can achieve the above object, and has completed the present invention.
すなわち、本発明は、下記の固体酸化物型燃料電池の燃料極用材料に係る。
１． 固体酸化物型燃料電池の燃料極に用いるための電極材料であって、
（１）前記材料は、第１成分として酸化ニッケル、第２成分として酸化ジルコニウム、ならびに第３成分として酸化スカンジウム、酸化イットリウム及び酸化カルシウムの少なくとも１種を含む組成を有し、
（２）前記材料は、細孔容積０．１〜１．５ｃｍ３／ｇの粉末である、
ことを特徴とする固体酸化物型燃料電池の燃料極用材料。
２． 前記材料の平均粒子径が０．１〜５μｍである、前記項１に記載の固体酸化物型燃料電池の燃料極用材料。
３． 前記組成が、（第１成分）：（第２成分＋第３成分）＝４０〜６０：６０〜４０（重量比）であり、（第２成分）：（第３成分）＝８０〜９８：２０〜２（モル％）である、前記項１又は２に記載の固体酸化物型燃料電池の燃料極用材料。
４． 第３成分の一部又は全部が第２成分に固溶している、前記項１〜３のいずれかに記載の固体酸化物型燃料電池の燃料極用材料。
５． 前記項１〜４のいずれかに記載の材料を用いて製造された燃料極を含む固体酸化物型燃料電池。
６． 前記燃料極の導電率が１９００Ｓ／ｃｍ以上であり、前記燃料極、１０Ｓｃ１ＣｅＳＺを用いた厚さ２００μｍの電解質基板及び空気極（ＬａＳｒＭｎＯ ３ ）で構成される燃料電池を、燃料；１１％Ｈ ２ Ｏ、８９％Ｈ ２ 、酸化剤；空気４倍等量、燃料利用率４０％、温度１０００℃の運転条件で発電評価したときの燃料電池としての最大出力が０．８０Ｗ／ｃｍ２以上である、前記項５に記載の固体酸化物型燃料電池。
That is, the present invention relates to a fuel electrode MATERIAL FOR solid oxide fuel cell below.
1. An electrode material for use in a fuel electrode of a solid oxide fuel cell,
(1) The material has a composition containing nickel oxide as a first component, zirconium oxide as a second component, and at least one of scandium oxide, yttrium oxide, and calcium oxide as a third component,
(2) The material is a powder having a pore volume of 0.1 to 1.5 cm 3 / g.
A material for a fuel electrode of a solid oxide fuel cell.
2. Item 2. The material for a fuel electrode of a solid oxide fuel cell according to Item 1, wherein the material has an average particle size of 0.1 to 5 µm.
3 . The composition is (first component) :( second component + third component) = 40-60: 60-40 (weight ratio), (second component) :( third component) = 80-98: Item 3. The fuel electrode material for a solid oxide fuel cell according to Item 1 or 2 , which is 20 to 2 (mol%).
4 . Item 4. The material for a fuel electrode of a solid oxide fuel cell according to any one of Items 1 to 3 , wherein a part or all of the third component is dissolved in the second component.
5 . 5. A solid oxide fuel cell including a fuel electrode manufactured using the material according to any one of Items 1 to 4 .
6 . A fuel cell having a conductivity of the fuel electrode of 1900 S / cm or higher, a fuel cell composed of the fuel electrode, a 200 μm thick electrolyte substrate using 10Sc1CeSZ, and an air electrode (LaSrMnO 3 ) is used as a fuel; 11% H 2 O , 89% H 2 , oxidizing agent; air equivalent to 4 times, fuel utilization rate 40%, maximum output as a fuel cell when operating under the operating conditions of a temperature of 1000 ° C. is 0.80 W / cm 2 or more, Item 6. The solid oxide fuel cell according to Item 5 .
本発明では、ＳＯＦＣ用アノード原料とそして、１）酸化ニッケル、２）酸化ジルコニウム、３）酸化スカンジウム、酸化イットリウム及び酸化カルシウムの少なくとも１種（好ましくは第２成分と第３成分はジルコニア固溶体として存在）を含む混合粉末において混合比、細孔容積等を炭酸化反応によりコントロールすることによって、高い導電性をもつ電極材料を与えることが可能となる。すなわち、ＳＯＦＣ用アノードに適した混合粉末を提供し、これによりＳＯＦＣの発電特性の向上を図ることができる。 In the present invention, the anode material for SOFC, and at least one of 1) nickel oxide, 2) zirconium oxide, 3) scandium oxide, yttrium oxide and calcium oxide (preferably the second component and the third component exist as a zirconia solid solution. It is possible to provide an electrode material having high conductivity by controlling the mixing ratio, pore volume, and the like in the mixed powder containing) by a carbonation reaction. That is, it is possible to provide a mixed powder suitable for the SOFC anode, thereby improving the power generation characteristics of the SOFC.
以下に、本発明に係るＳＯＦＣ用燃料極材料の製法及びＳＯＦＣ用燃料極材料、それを原料に用いた燃料極について詳細に説明する。 Hereinafter, a method for producing a fuel electrode material for SOFC, a fuel electrode material for SOFC, and a fuel electrode using the same as a raw material will be described in detail.
１．固体酸化物型燃料電池の燃料極用材料
本発明の燃料極用材料は、固体酸化物型燃料電池の燃料極に用いるための電極材料であって、
（１）前記材料は、第１成分として酸化ニッケル、第２成分として酸化ジルコニウム、ならびに第３成分として酸化スカンジウム、酸化イットリウム及び酸化カルシウムの少なくとも１種を含む組成を有し、
（２）前記材料は、細孔容積０．１ｃｍ３／ｇ以上であり、かつ、気孔率２０％以上である粉末である、
ことを特徴とする。
1. The material for a fuel electrode of a solid oxide fuel cell The material for a fuel electrode of the present invention is an electrode material for use in a fuel electrode of a solid oxide fuel cell,
(1) The material has a composition containing nickel oxide as a first component, zirconium oxide as a second component, and at least one of scandium oxide, yttrium oxide, and calcium oxide as a third component,
(2) The material is a powder having a pore volume of 0.1 cm 3 / g or more and a porosity of 20% or more.
It is characterized by that.
組成
本発明材料は、第１成分として酸化ニッケル、第２成分として酸化ジルコニウム、ならびに第３成分として酸化スカンジウム、酸化イットリウム及び酸化カルシウムの少なくとも１種を含む組成を有する。
Composition The material of the present invention has a composition containing nickel oxide as the first component, zirconium oxide as the second component, and at least one of scandium oxide, yttrium oxide and calcium oxide as the third component.
本発明材料では、これら第１成分〜第３成分を含む組成として示すことができる限り、これら酸化物が互いに固溶した状態で存在していても良いし、固溶していなくても良い。例えば、第３成分の一部又は全部が第２成分に固溶して安定化ジルコニアを構成していても良い。この場合、第１成分は、独立した酸化物相（酸化ニッケル相）として存在していても良い。すなわち、本発明材料は、酸化ニッケル相と安定化ジルコニア相の２相から構成されている混合酸化物も包含される。 In the material of the present invention, as long as it can be shown as a composition containing these first to third components, these oxides may exist in a state of solid solution with each other or may not be in solution. For example, a part or all of the third component may be dissolved in the second component to constitute stabilized zirconia. In this case, the first component may exist as an independent oxide phase (nickel oxide phase). That is, the material of the present invention includes a mixed oxide composed of two phases of a nickel oxide phase and a stabilized zirconia phase.
第１成分〜第３成分の割合は限定的ではないが、一般的には（第１成分）：（第２成分＋第３成分）＝４０〜６０：６０〜４０（重量比）であり、（第２成分）：（第３成分）＝８０〜９８：２０〜２（モル％）であることが好ましい。かかる範囲内に設定することによって、発電時におけるＮｉの凝集を効果的に抑制ないしは防止でき、所望のＮｉネットワーク（導電経路）を確保することによって、より高い導電性ひいては高い発電効率を得ることが可能となる。 The ratio of the first component to the third component is not limited, but is generally (first component) :( second component + third component) = 40-60: 60-40 (weight ratio), (Second component): (Third component) = 80 to 98:20 to 2 (mol%) is preferable. By setting within this range, Ni aggregation during power generation can be effectively suppressed or prevented, and by securing a desired Ni network (conductive path), higher conductivity and thus higher power generation efficiency can be obtained. It becomes possible.
本発明では、特に第２成分と第３成分との比率は、第３成分の種類に応じて適宜設定することが望ましい。これにより、より効率良く安定化ジルコニアを調製することが可能になる。例えば、第３成分が酸化イットリウムの場合はＺｒＯ２：Ｙ２Ｏ３＝９０〜９８：１０〜２モル％、第３成分が酸化スカンジウムの場合はＺｒＯ２：Ｓｃ２Ｏ３＝８９〜９６：１１〜４モル％、第３成分が酸化カルシウムの場合はＺｒＯ２：ＣａＯ＝８０〜９５：２０〜５モル％になるように調整することが好ましい。 In the present invention, it is desirable to set the ratio of the second component and the third component as appropriate according to the type of the third component. This makes it possible to prepare stabilized zirconia more efficiently. For example, when the third component is yttrium oxide, ZrO 2 : Y 2 O 3 = 90 to 98:10 to 2 mol%, and when the third component is scandium oxide, ZrO 2 : Sc 2 O 3 = 89 to 96: 11-4 mol%, in the case of the third component is calcium oxide ZrO 2: CaO = 80~95: 20~5 is preferably adjusted so that the mole%.
また、本発明材料では、必要に応じて第１成分〜第３成分以外の成分（添加剤）を含んでいても良い。例えば、酸化セリウム、酸化イッテリビウム、酸化サマリウムなどの３A族に属する元素、または酸化アルミニウム等を挙げることができる。この場合の添加剤の含有量は、第１成分〜第３成分の合計が本発明材料中９０〜１００重量％、特に９５〜１００重量％となるように設定すれば良い。 Moreover, in this invention material, components (additives) other than a 1st component-a 3rd component may be included as needed. For example, elements belonging to Group 3A such as cerium oxide, ytterbium oxide, and samarium oxide, aluminum oxide, and the like can be given. The content of the additive in this case may be set so that the total of the first to third components is 90 to 100% by weight, particularly 95 to 100% by weight, in the material of the present invention.
細孔容積及び気孔率
本発明材料は、細孔容積０．１ｃｍ３／ｇ以上であり、かつ、気孔率２０％以上である粉末である。
Pore volume and porosity The material of the present invention is a powder having a pore volume of 0.1 cm 3 / g or more and a porosity of 20% or more.
細孔容積は、通常は０．１ｃｍ３／ｇ以上であり、好ましくは０．１〜１．５ｃｍ３／ｇ、より好ましくは０．１〜１．０ｃｍ３／ｇである。細孔容積が小さすぎる場合、燃料ガスがアノード内部を通り電解質界面へ十分に供給されず発電効率が低下する。細孔容積が大きすぎる場合は、構造体として空隙部分がアノードの大多数を占め、その結果として導電パスが確保されず、アノードそのものの導電率が低下する。 The pore volume is usually 0.1 cm 3 / g or more, preferably 0.1 to 1.5 cm 3 / g, more preferably 0.1 to 1.0 cm 3 / g. If the pore volume is too small, the fuel gas will not be sufficiently supplied to the electrolyte interface through the inside of the anode, resulting in a decrease in power generation efficiency. When the pore volume is too large, the void portion occupies the majority of the anode as a structure, and as a result, a conductive path is not secured and the conductivity of the anode itself is lowered.
気孔率は、通常は２０％以上であり、好ましくは２０〜５０％、より好ましくは２０〜４０％である。気孔率が２０％未満である場合は燃料ガスがアノード内部を通り電解質界面へ到達する際に、十分なガス流速が得られず、単位時間当たりの発電効率の低下となるので好ましくない。 The porosity is usually 20% or more, preferably 20 to 50%, more preferably 20 to 40%. When the porosity is less than 20%, when the fuel gas passes through the anode and reaches the electrolyte interface, a sufficient gas flow rate cannot be obtained, resulting in a decrease in power generation efficiency per unit time.
その他の物性
本発明材料（粉末）では、平均粒子径は特に限定的ではないが、一般的には０．１〜５μｍ程度の範囲内であることが好ましい。上記範囲内に設定することによって、より高い導電性を得ることができる。
Other Physical Properties In the material of the present invention (powder), the average particle size is not particularly limited, but generally it is preferably in the range of about 0.1 to 5 μm. By setting within the above range, higher conductivity can be obtained.
本発明の材料は、固体酸化物型燃料電池の燃料極用として好適に用いることができる。その使用方法は、公知の電極材料と同様にすれば良い。例えば、本発明材料を含むスラリー又はペーストを調製し、その皮膜を電解質基板上に形成し、乾燥した後 、焼成し、次いで還元処理することによって、最終的に電極を得ることができる。スラリー又はペーストの調製においては、必要に応じて、樹脂バインダー、消泡剤、溶媒、界面活性剤等の公知の添加剤を配合することができる。 The material of the present invention can be suitably used for a fuel electrode of a solid oxide fuel cell. The usage method may be the same as that of a known electrode material. For example, an electrode can be finally obtained by preparing a slurry or paste containing the material of the present invention, forming a film on the electrolyte substrate, drying, firing, and then reducing treatment. In preparing the slurry or paste, known additives such as a resin binder, an antifoaming agent, a solvent, and a surfactant can be blended as necessary.
２．固体酸化物型燃料電池の燃料極用材料の製造方法
本発明の製造方法は、固体酸化物型燃料電池の燃料極用材料を製造する方法であって、
（１）ａ）ニッケルイオン、ｂ）ジルコニウムイオン、ならびにｃ）スカンジウムイオン、イットリウムイオン及びカルシウムイオンの少なくとも１種のイオンを含む混合溶液を調製する第１工程、
（２）前記溶液に炭酸ガスを供給しながら前記溶液から沈殿物を生成させる第２工程、及び
（３）前記沈殿物を焼成する第３工程、
を含むことを特徴とする。
2. Manufacturing method of fuel electrode material of solid oxide fuel cell The manufacturing method of the present invention is a method of manufacturing a fuel electrode material of a solid oxide fuel cell,
(1) a first step of preparing a mixed solution containing a) nickel ions, b) zirconium ions, and c) at least one ion of scandium ions, yttrium ions, and calcium ions,
(2) a second step of generating a precipitate from the solution while supplying carbon dioxide gas to the solution, and (3) a third step of firing the precipitate.
It is characterized by including.
第１工程
第１工程では、ａ）ニッケルイオン、ｂ）ジルコニウムイオン、ならびにｃ）スカンジウムイオン、イットリウムイオン及びカルシウムイオンの少なくとも１種のイオンを含む混合溶液を調製する。
First Step In the first step, a mixed solution containing a) nickel ions, b) zirconium ions, and c) at least one ion of scandium ions, yttrium ions and calcium ions is prepared.
混合溶液の調製に際しては公知の方法に従えば良く、例えば適当な溶媒にこれらイオンの供給源となる化合物を溶解させることによって混合溶液を得ることができる。特に、本発明では、溶媒として水又は水系溶媒が好ましく、特に水を好適に用いることができる。 In preparing the mixed solution, a known method may be followed. For example, a mixed solution can be obtained by dissolving a compound serving as a source of these ions in an appropriate solvent. In particular, in the present invention, water or an aqueous solvent is preferable as the solvent, and water can be particularly preferably used.
イオンの供給源となる化合物は、これらのイオン種を含む化合物を使用すれば良い。特に、塩類（塩化物、硝酸塩、硫酸塩、酢酸塩、炭酸塩等の無機酸塩又は有機酸塩）を好適に使用することができる。従って、ニッケルイオンの供給源としては、例えば塩化ニッケル、硝酸ニッケル、硫酸ニッケル、酢酸ニッケル等の少なくとも１種を挙げることができる。ジルコニウムイオンの供給源としては、例えばオキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、硫酸ジルコニウム、酢酸ジルコニウム等の少なくとも１種を挙げることができる。スカンジウムイオンの供給源としては、例えば塩化スカンジウム、硝酸スカンジウム硫酸スカンジウム、酢酸スカンジウム等の少なくとも１種を挙げることができる。イットリウムイオンの供給源としては、例えば塩化イットリウム、硝酸イットリウム、硫酸イットリウム、酢酸イットリウム等の少なくとも１種を挙げることができる。カルシウムイオンの供給源として、例えば塩化カルシウム、硝酸カルシウム、酢酸カルシウム等の少なくとも１種を挙げることができる。 As a compound serving as an ion supply source, a compound containing these ionic species may be used. In particular, salts (inorganic acid salts or organic acid salts such as chlorides, nitrates, sulfates, acetates and carbonates) can be preferably used. Accordingly, examples of the nickel ion supply source include at least one of nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, and the like. Examples of the supply source of zirconium ions include at least one of zirconium oxychloride, zirconium oxynitrate, zirconium sulfate, zirconium acetate, and the like. Examples of the supply source of scandium ions include at least one of scandium chloride, scandium nitrate, scandium sulfate, and scandium acetate. Examples of the supply source of yttrium ions include at least one of yttrium chloride, yttrium nitrate, yttrium sulfate, yttrium acetate, and the like. Examples of the calcium ion supply source include at least one of calcium chloride, calcium nitrate, calcium acetate, and the like.
これらの化合物は、用いる溶媒の種類等に応じて適宜選択することができる。例えば、溶媒として水を用いる場合は、水溶性化合物（水溶性塩）を使用すれば良い。 These compounds can be appropriately selected according to the type of solvent used. For example, when water is used as the solvent, a water-soluble compound (water-soluble salt) may be used.
これらの配合割合は、例えば前記の本発明材料の組成となるように適宜設定すれば良い。また、混合溶液中における各成分の濃度は、酸化物換算で０．１〜２０重量％の範囲内で適宜設定すれば良い。 What is necessary is just to set these compounding ratios suitably so that it may become a composition of the said this invention material, for example. Moreover, what is necessary is just to set suitably the density | concentration of each component in a mixed solution within the range of 0.1-20 weight% in conversion of an oxide.
混合溶液の調製に関して、その配合順序等は限定されない。１つの溶媒に第１成分〜第３成分の供給源を配合しても良いし、あるいは別々に溶液を調製した後にこれらの溶液を混合する方法であっても良い。特に、本発明では、予め、ａ）ニッケルイオンを含む第１溶液と、ｂ）ジルコニウムイオン、ならびにｃ）スカンジウムイオン、イットリウムイオン及びカルシウムイオンの少なくとも１種のイオンを含む第２溶液とを調製した後、両者を混合することにより前記混合溶液を調製することが好ましい。この場合は、第１溶液のＮｉ濃度はＮｉＯ換算で１〜１０重量％程度とすることが好ましい。また、第２溶液のＺｒ濃度はＺｒＯ２換算で１〜１０重量％程度とすることが好ましい。 Regarding the preparation of the mixed solution, the blending order and the like are not limited. The supply source of the first component to the third component may be blended in one solvent, or a method of mixing these solutions after separately preparing the solutions may be used. In particular, in the present invention, a) a first solution containing nickel ions and b) a zirconium ion and c) a second solution containing at least one ion of scandium ion, yttrium ion and calcium ion were prepared in advance. Then, it is preferable to prepare the said mixed solution by mixing both. In this case, the Ni concentration of the first solution is preferably about 1 to 10% by weight in terms of NiO. Further, Zr concentration in the second solution is preferably about 1 to 10 wt% in terms of ZrO 2.
第２工程
第２工程では、前記溶液に炭酸ガスを供給しながら前記溶液から沈殿物を生成させる。
Second Step In the second step, a precipitate is generated from the solution while supplying carbon dioxide gas to the solution.
第２工程を実行する方法は特に限定されないが、例えば１）前記溶液に炭酸アルカリを添加することにより、炭酸ガスを発生させるとともに炭酸塩を沈殿物として生成させる方法、２）別途に用意した炭酸ガスを前記溶液中にバブリングしながら前記溶液にアルカリを添加して沈殿物を生成させる方法、３）前記工程で炭酸塩を用いた場合には、それに塩酸や硝酸などの酸を加え一旦溶解させ、そこに炭酸アルカリを添加し、再度、炭酸塩を得る方法等が挙げられる。 The method for performing the second step is not particularly limited. For example, 1) a method for generating carbon dioxide and generating carbonate as a precipitate by adding an alkali carbonate to the solution, and 2) a separately prepared carbonic acid. A method of adding alkali to the solution while bubbling gas into the solution to produce a precipitate. 3) When carbonate is used in the above step, add an acid such as hydrochloric acid or nitric acid to dissolve it once. And a method of adding an alkali carbonate to obtain a carbonate again.
特に、本発明では、前記１）の方法が好ましい。以下、前記１）の方法についてより具体的に説明する。炭酸アルカリとしては、例えば炭酸水素ナトリウム、炭酸ナトリウム、炭酸水素アンモニウム、炭酸アンモニウム、炭酸カリウム等の少なくとも１種を用いることができるが、特に炭酸水素アルカリが好ましい。炭酸アルカリの添加量は、沈殿物を生成させるのに十分な量とすれば良い。 In particular, in the present invention, the method 1) is preferable. Hereinafter, the method 1) will be described more specifically. As the alkali carbonate, for example, at least one of sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, potassium carbonate and the like can be used, and alkali hydrogen carbonate is particularly preferable. The amount of alkali carbonate added may be sufficient to produce a precipitate.
炭酸アルカリは、そのまま添加しても良いし、適当な溶媒に溶解させて溶液の状態で添加することもできる。例えば、炭酸アルカリ水溶液として好適に用いることができる。溶液として用いる場合、その濃度は特に限定されないが、通常は１０〜２０重量％程度とすれば良い。 The alkali carbonate may be added as it is, or may be added in the form of a solution after dissolving in an appropriate solvent. For example, it can be suitably used as an aqueous alkali carbonate solution. When used as a solution, the concentration is not particularly limited, but it is usually about 10 to 20% by weight.
前記１）の方法において、硝酸ニッケル、オキシ硝酸ジルコニウムを用い、炭酸アルカリとして炭酸水素ナトリウムを用いる場合、次のような反応が起こる。 In the method 1), when nickel nitrate and zirconium oxynitrate are used and sodium hydrogen carbonate is used as the alkali carbonate, the following reaction occurs.
Ni(NO3)2＋NaHCO3 →NiCO3+ NaNO3+HNO3
ZrO(NO3)2＋NaHCO3→ ZrOCO３+NaNO3+HNO3
さらに、第３成分の供給源として硝酸スカンジウム、硝酸イットリウム又は硝酸カルシウムのうちいずれかを選択した場合は、それぞれ次の反応が起こる。
Ni (NO 3 ) 2 + NaHCO 3 → NiCO 3 + NaNO 3 + HNO 3
ZrO (NO 3 ) 2 + NaHCO 3 → ZrOCO 3 + NaNO 3 + HNO 3
Furthermore, when any one of scandium nitrate, yttrium nitrate, or calcium nitrate is selected as the third component supply source, the following reactions occur.
2Sc(NO3)3 + 3NaHCO3 → Sc2(CO3)3+3NaNO3+3HNO3
2Y(NO3)3 + 3NaHCO3 → Y2(CO3)3+3NaNO3+3HNO3
Ca(NO3)2 + NaHCO3 → CaCO3 +NaNO3+HNO3
また、フリーの硝酸が生成されることから、
NaHCO3+HNO3→NaNO3+H2O+CO2↑
の反応も同時に起こり、ＣＯ２ガスが発生している。
2Sc (NO 3 ) 3 + 3 NaHCO 3 → Sc 2 (CO 3 ) 3 +3 NaNO 3 + 3HNO 3
2Y (NO 3 ) 3 + 3 NaHCO 3 → Y 2 (CO 3 ) 3 +3 NaNO 3 + 3HNO 3
Ca (NO 3 ) 2 + NaHCO 3 → CaCO3 + NaNO 3 + HNO 3
Since free nitric acid is produced,
NaHCO 3 + HNO 3 → NaNO 3 + H 2 O + CO 2 ↑
At the same time, CO 2 gas is generated.
本発明では、炭酸アルカリによる炭酸化反応時に発生するＣＯ２ガスを利用し、炭酸化により得られる混合炭酸塩にＣＯ２ガスが混入し、粒子間の空隙を形成させることを積極的に利用したものである。 In the present invention, the CO 2 gas generated during the carbonation reaction with the alkali carbonate is used, and the mixed carbonate obtained by the carbonation is mixed with the CO 2 gas and actively used to form voids between the particles. Is.
通常の炭酸アルカリを使用する炭酸化反応の場合は、前述の反応のようにＣＯ２ガスが発生しても、大気に放出されていることは既知である。ところが、この発生する炭酸ガスを反応溶液中に可能な限り溶解させ、またスラリー中にＣＯ２ガスを多く含ませることにより、得られる沈殿物中に化学反応によるＣＯ３ −２以外に、ＣＯ２ガスが吸着される。 In the case of a carbonation reaction using a normal alkali carbonate, it is known that even if CO 2 gas is generated as in the above-described reaction, it is released to the atmosphere. However, the carbon dioxide gas to the generated dissolved as much as possible in the reaction solution, and by including a large amount of CO 2 gas into the slurry, in addition to CO 3 -2 by a chemical reaction in the resulting precipitate, CO 2 Gas is adsorbed.
また、発生するＣＯ２ガスを可能な限り溶解させるためには、混合溶液の温度を２０℃以下、特に１０℃以下にすることが望ましい。溶解度が低温である方が上がるためであり、この反応系の場合では正確な溶解度は不明であるが、水に対するＣＯ２の溶解度は、２０℃の場合は水１Ｌ当たりＣＯ２ガスが０．８８Ｌ、１０℃の場合は水１Ｌ当たり１．１９ＬのＣＯ２ガスが溶解するため、これに比例して温度が低い方がより多くのＣＯ２ガスを溶解させることができる。 In order to dissolve the generated CO 2 gas as much as possible, the temperature of the mixed solution is desirably 20 ° C. or less, particularly 10 ° C. or less. This is because the solubility is lower when the temperature is lower. In this reaction system, the exact solubility is unknown, but the solubility of CO 2 in water is 0.88 L of CO 2 gas per liter of water at 20 ° C. In the case of 10 ° C., 1.19 L of CO 2 gas dissolves per liter of water, and therefore, a larger amount of CO 2 gas can be dissolved in proportion to the lower temperature.
ＣＯ２ガスの溶解度を上げる方法としては、例えば耐圧容器内で反応させ、発生するＣＯ２ガスにより加圧状態化でスラリー中に溶解させる方法等が有効である。この反応系の場合も、発生するＣＯ２ガスの溶解度は、反応溶液中に無機塩類が溶解しているので正確な値は不明であるが、一般的に炭酸水を製造させるときにＮａＣｌ等の無機塩を添加させ溶解度を向上させていることから、純水での溶解度より確実に上がっていることが推定できる。 As a method for increasing the solubility of the CO 2 gas, for example, a method of reacting in a pressure vessel and dissolving it in the slurry in a pressurized state with the generated CO 2 gas is effective. In the case of this reaction system as well, the solubility of the generated CO 2 gas is unknown because the inorganic salts are dissolved in the reaction solution. Since the solubility is improved by adding an inorganic salt, it can be presumed that the solubility is surely higher than the solubility in pure water.
さらに、多く混合炭酸塩中に混入させる反応方法として、炭酸アルカリを大過剰に添加する方法も有効である。大過剰の炭酸アルカリに含まれる、炭酸化反応が終了した後に、反応溶液中にクエン酸を添加することによりＣＯ３ ２−を分解してＣＯ２ガスとして発生させてもよい。この反応を積極的に利用して、炭酸化した沈殿物にＣＯ２ガスを吸着させ、より確実に細孔を確保することができる。 Furthermore, a method of adding a large excess of alkali carbonate is also effective as a reaction method for mixing a large amount in the mixed carbonate. After the carbonation reaction contained in a large excess of alkali carbonate is completed, CO 3 2− may be decomposed and generated as CO 2 gas by adding citric acid to the reaction solution. By actively utilizing this reaction, CO 2 gas can be adsorbed to the carbonated precipitate, and the pores can be secured more reliably.
第３工程
第３工程では、前記沈殿物を焼成する。焼成温度は、通常７００〜１４００℃とし、好ましくは９００〜１１００℃である。また、焼成雰囲気は、限定的ではないが、通常は大気中又は酸化性雰囲気とすれば良い。
Third Step In the third step, the precipitate is fired. The firing temperature is usually 700 to 1400 ° C, preferably 900 to 1100 ° C. Further, the firing atmosphere is not limited, but it may be usually in the air or an oxidizing atmosphere.
本発明の１つの特徴として、炭酸化された沈殿物をそのまま焼成することにより、ＣＯ２ガスを分解発生させ、そのガスにより細孔を確保する点にある。炭酸化した沈殿物を焼成することによって例えば次のような反応が起こる。 One feature of the present invention is that the carbonated precipitate is fired as it is, so that CO 2 gas is decomposed and pores are secured by the gas. For example, the following reaction occurs by baking the carbonated precipitate.
NiCO3 → NiO ＋ CO2
ZrOCO３ → ZrO2 ＋ CO2
Sc2(CO3)3 → Sc2O3 ＋ 3CO2
本発明において所望の細孔が確保される正確なメカニズムは不明であるが、おそらく焼成時にＮｉネットワークが形成される過程で、発生ガスによる物理的な細孔が形成されると考えられる。
NiCO 3 → NiO + CO 2
ZrOCO 3 → ZrO 2 + CO 2
Sc 2 (CO 3 ) 3 → Sc 2 O 3 + 3CO 2
The exact mechanism by which the desired pores are secured in the present invention is unknown, but it is considered that physical pores are formed by the generated gas in the process of forming the Ni network during firing.
以下、実施例及び比較例を示し、本発明の特徴をより詳細に説明する。ただし、本発明は、実施例の範囲に限定されるものではない。 Examples and comparative examples will be shown below to describe the features of the present invention in more detail. However, the present invention is not limited to the scope of the examples.
本発明にかかわる実施例、比較例で使用された酸化ニッケルの前駆体と安定化ジルコニアを生成させる前駆体の製造条件は、以下のとおりである。 The production conditions of the nickel oxide precursor and the precursor for producing stabilized zirconia used in Examples and Comparative Examples according to the present invention are as follows.
なお、本発明の実施例及び比較例で用いた結晶相、平均粒径、細孔容積及び比表面積の評価方法は、以下の通りである。
（１） 平均粒径の測定： レーザー回析散乱法によるＳＡＬＡＤ−２０００装置（島津製作所製）で行った。
（２） 細孔容積の測定： 細孔分布測定装置（Quantachrome社製）で行った。
（３） 比表面積の測定： ＢＥＴ法のフローブ２３００型（マイクロメリテックス社製）で行った。
In addition, the evaluation method of the crystal phase, average particle diameter, pore volume, and specific surface area used in Examples and Comparative Examples of the present invention is as follows.
(1) Measurement of average particle diameter: It was carried out with a SALAD-2000 apparatus (manufactured by Shimadzu Corporation) by a laser diffraction scattering method.
(2) Measurement of pore volume: It was measured with a pore distribution measuring device (manufactured by Quantachrome).
(3) Measurement of specific surface area: The measurement was performed with a BET-type flow 2300 (manufactured by Micromeritex).
混合溶液調製例１
１）酸化ニッケルの前駆体
ニッケルの可溶性塩として市販の硝酸ニッケルの結晶をイオン交換水にてＮｉＯ濃度１０重量％になるように調整した。（Ａ液）
２）安定化ジルコニアを生成させる前駆体
安定化ジルコニアを生成させる前駆体の可溶性塩として、第一稀元素化学工業（株）製の硝酸ジルコニウム水溶液に、同じく第一稀元素化学工業（株）製の硝酸スカンジウム結晶を添加し、イオン交換水にてＺｒＯ２濃度５．２７重量％になるように調整した。なお、このとき、ＺｒＯ２とＳｃ２Ｏ３との混合比率として８９：１１モル％になるように硝酸スカンジウム結晶を添加した。（混合Ｂ液）
３）混合溶液の調製
硝酸ニッケル水溶液（Ａ液）５１０ｇと安定化ジルコニアを生成させる前駆体の溶液（混合Ｂ液）６００ｇを混合した（以下 Ｃ液）。このとき、Ｃ液中には、ＮｉＯ：（ＺｒＯ２＋Ｓｃ２Ｏ３） ＝５１：６０重量比となり、ＮｉＯをＮｉ換算するとＮｉ：ＺｒＯ２＝４０：６０重量比であった。以下、実施例でＣ液を用いた。
Mixed solution preparation example 1
1) Precursor of nickel oxide A commercially available nickel nitrate crystal as a soluble nickel salt was adjusted with ion-exchanged water so as to have a NiO concentration of 10% by weight. (Liquid A)
2) Precursor for producing stabilized zirconia As a soluble salt of the precursor for producing stabilized zirconia, a zirconium nitrate aqueous solution made by Daiichi Rare Element Chemical Industry Co., Ltd. was also used. Scandium nitrate crystals were added, and the ZrO 2 concentration was adjusted to 5.27 wt% with ion-exchanged water. At this time, scandium nitrate crystals were added so that the mixing ratio of ZrO 2 and Sc 2 O 3 was 89:11 mol%. (Mixed B liquid)
3) Preparation of mixed solution 510 g of a nickel nitrate aqueous solution (A liquid) and 600 g of a precursor solution (mixed B liquid) for producing stabilized zirconia were mixed (hereinafter referred to as C liquid). At this time, in the liquid C, NiO: (ZrO 2 + Sc 2 O 3 ) = 51: 60 weight ratio, and NiO converted to Ni was Ni: ZrO 2 = 40: 60 weight ratio. Hereinafter, C liquid was used in the Example.
実施例１
１０℃に液温を保持した前記Ｃ液をビーカーに入れて攪拌しながら、市販の炭酸水素ナトリウム粉末を少量ずつ添加した。このとき、発泡状態を観察しながら炭酸水素ナトリウム粉末を添加した。やがて、発泡しながら沈殿が析出し、さらに添加を続けると、ＣＯ２ガスの発生が起こらなくなった。この時点で、攪拌を中止して、静置させ、沈殿を沈降させた。
Example 1
Commercially available sodium hydrogencarbonate powder was added little by little while stirring the liquid C, which was kept at 10 ° C., in a beaker. At this time, sodium hydrogen carbonate powder was added while observing the foamed state. Eventually, precipitation occurred while foaming, and when the addition was continued, generation of CO 2 gas did not occur. At this point, stirring was stopped and allowed to stand to precipitate the precipitate.
この沈殿物を含むスラリーをデカンテーション法により数回洗浄させ、未溶解の炭酸水素ナトリウムと溶解したＮａイオンとを除去した。その後、ヌッチェにて吸引ろ過を行い、沈殿物と分別した。このとき得られた水分を含んだ沈殿物は１３５０ｇであった。 The slurry containing the precipitate was washed several times by a decantation method to remove undissolved sodium bicarbonate and dissolved Na ions. Thereafter, suction filtration was performed with Nutsche to separate from precipitates. The water-containing precipitate obtained at this time was 1350 g.
得られた沈殿物を大気中１０００℃にて焼成した後、ＹＳＺボール、イオン交換水とともにポリエチレン製ポットに入れ、２４時間ボールミル粉砕した後、乾燥させることによって、ＮｉＯと安定化ジルコニアとの混合酸化物８７ｇを得た。この混合酸化物は、細孔容積０．４５ｃｍ３／ｇであり、平均粒子径が０．３μｍであった。 After the obtained precipitate was baked at 1000 ° C. in the atmosphere, it was put into a polyethylene pot together with YSZ balls and ion-exchanged water, ball milled for 24 hours, and then dried to mix and oxidize NiO and stabilized zirconia. 87 g of product was obtained. This mixed oxide had a pore volume of 0.45 cm 3 / g and an average particle size of 0.3 μm.
実施例２
Ｃ液を加圧反応容器に入れ、攪拌しながら炭酸水素ナトリウム水溶液（１０重量％）を徐々に添加した。このとき、液温を１０℃に保持し、実施例１と同様、ＣＯ２ガスが発泡するので、容器上部に発泡面が上がらないように添加した。実施例１と同様に発泡しながら沈殿が析出した。ＣＯ２ガスの発泡が起こらなくなった時点で、炭酸水素ナトリウム水溶液の添加を終了した。このとき、容器内圧力は２．２ｋｇｆ／ｃｍ３であった。
Example 2
Solution C was placed in a pressure reaction vessel, and an aqueous sodium hydrogen carbonate solution (10% by weight) was gradually added while stirring. At this time, the liquid temperature was maintained at 10 ° C., and CO 2 gas was foamed as in Example 1. Therefore, the foam was added to the upper part of the container so as not to rise. A precipitate was deposited while foaming in the same manner as in Example 1. The addition of the aqueous sodium hydrogen carbonate solution was terminated when no CO 2 gas bubbling occurred. At this time, the internal pressure of the container was 2.2 kgf / cm 3 .
そして、攪拌を中止して、静置させ、沈殿を沈降させた。この沈殿物を含むスラリーを実施例１と同様にデカンテーション法により数回洗浄させてＮａイオンを除去した。その後、ヌッチェにて吸引ろ過を行い、沈殿物と分別した。このとき得られた水分を含んだ沈殿物は１３４０ｇであった。 And stirring was stopped and it was left still and the precipitate was settled. The slurry containing this precipitate was washed several times by the decantation method in the same manner as in Example 1 to remove Na ions. Thereafter, suction filtration was performed with Nutsche to separate from precipitates. The precipitate containing water obtained at this time was 1340 g.
得られた沈殿物を大気中１０００℃にて焼成し、その後、ＹＳＺボール、イオン交換水とともにポリエチレン製ポットに入れ、２４時間ボールミル粉砕した後、乾燥させることにより、ＮｉＯと安定化ジルコニアとの混合酸化物９０ｇを得た。この混合酸化物は、細孔容積０．６０ｃｍ３／ｇであり、平均粒子径が０．２５μｍであった。 The obtained precipitate was baked at 1000 ° C. in the atmosphere, then put into a polyethylene pot together with YSZ balls and ion-exchanged water, ball milled for 24 hours, and then dried to mix NiO and stabilized zirconia. 90 g of oxide was obtained. This mixed oxide had a pore volume of 0.60 cm 3 / g and an average particle size of 0.25 μm.
実施例３
２０℃に液温を保持した炭酸水素ナトリウム水溶液（１０重量％）を調製し、この溶液５０００ｇに徐々にＣ液１１００ｇを添加した。このとき、実施例１と同様にＣＯ２ガスが発泡するので、容器上部に発泡面が上がらないように添加した。実施例１と同様に発泡しながら沈殿が析出した。ＣＯ２ガスの発泡が起こらなくなった時点で、炭酸水素ナトリウム水溶液の添加を終了した。そして、攪拌を中止して、静置させ、沈殿物を沈降させた。
Example 3
A sodium hydrogen carbonate aqueous solution (10% by weight) maintaining the liquid temperature at 20 ° C. was prepared, and 1100 g of C liquid was gradually added to 5000 g of this solution. At this time, since CO 2 gas foams in the same manner as in Example 1, it was added so that the foamed surface did not rise above the container. A precipitate was deposited while foaming in the same manner as in Example 1. The addition of the aqueous sodium hydrogen carbonate solution was terminated when no CO 2 gas bubbling occurred. And stirring was stopped, it was left still and the deposit was settled.
この沈殿物を含むスラリーを実施例１と同様にデカンテーション法により数回洗浄させ、Ｎａイオンを除去した。その後、ヌッチェにて吸引ろ過を行い、沈殿物と分別した。このとき得られた水分を含んだ沈殿物は１５４０ｇであった。 The slurry containing this precipitate was washed several times by the decantation method in the same manner as in Example 1 to remove Na ions. Thereafter, suction filtration was performed with Nutsche to separate from precipitates. The water-containing precipitate obtained at this time was 1540 g.
得られた沈殿物を大気中１０００℃にて焼成した後、ＹＳＺボール、イオン交換水とともにポリエチレン製ポットに入れ、２４時間ボールミル粉砕した後、乾燥させることにより、ＮｉＯと安定化ジルコニアとの混合酸化物８３ｇを得た。この混合酸化物は、細孔容積が０．１０ｃｍ３／ｇであり、平均粒子径が５．０μｍであった。 After firing the resulting precipitate at 1000 ° C. in the atmosphere, it is put in a polyethylene pot together with YSZ balls and ion-exchanged water, ball milled for 24 hours, and then dried to mix and oxidize NiO and stabilized zirconia. 83 g of product was obtained. This mixed oxide had a pore volume of 0.10 cm 3 / g and an average particle size of 5.0 μm.
比較例１
平均粒子径１ミクロンの（株）田中化学研究所製ＮｉＯ ５１ｇと、平均粒子径０．５ミクロンの第一稀元素化学工業（株）製１１モル％スカンジア安定化ジルコニア６０ｇ（以下 １１ＳｃＳＺ）とを、ＹＳＺボール、エタノールとともにポリエチレン製ポットに入れ、２４時間ボールミルにより混合をした。
Comparative Example 1
51 g NiO manufactured by Tanaka Chemical Research Co., Ltd. with an average particle size of 1 micron and 60 g of 11 mol% scandia-stabilized zirconia (hereinafter referred to as 11ScSZ) manufactured by Daiichi Rare Element Chemical Co., Ltd. with an average particle size of 0.5 microns. , YSZ balls and ethanol were put together in a polyethylene pot and mixed by a ball mill for 24 hours.
ボールミルによって得られたスラリーを乾燥させた後、大気中１０００℃にて焼成した後、ＹＳＺボール、イオン交換水とともにポリエチレン製ポットに入れ、２４時間ボールミル粉砕した後、乾燥させることにより、ＮｉＯと安定化ジルコニアとの混合酸化物１０３ｇを得た。この混合酸化物は、細孔容積０．０５ｃｍ３／ｇであり、平均粒子径が０．７μｍであった。 After drying the slurry obtained by the ball mill, after firing at 1000 ° C. in the atmosphere, put it in a polyethylene pot with YSZ balls and ion-exchanged water, ball milling for 24 hours, and drying to stabilize NiO. 103 g of mixed oxide with zirconia bromide was obtained. This mixed oxide had a pore volume of 0.05 cm 3 / g and an average particle size of 0.7 μm.
比較例２
平均粒子径１０μｍの（株）田中化学研究所製ＮｉＯ ５１ｇと、平均粒子径０．５ミクロンの第一稀元素化学工業（株）製 １１ＳｃＳＺ ６０ｇとを、比較例１と同様に２４時間ボールミルにより混合をした。
Comparative Example 2
NiO 51g manufactured by Tanaka Chemical Research Co., Ltd. having an average particle diameter of 10 μm and 11ScSZ 60g manufactured by Daiichi Rare Element Chemicals Co., Ltd. having an average particle diameter of 0.5 μm were ball-milled for 24 hours as in Comparative Example 1. Mixed.
そして、ボールミルによって得られたスラリーを乾燥させた後、比較例１と同様に大気中１０００℃にて焼成した後、２４時間ボールミル粉砕した後、乾燥させることによって、ＮｉＯと安定化ジルコニアの混合酸化物１０５ｇを得た。この混合酸化物は、細孔容積０．０１ｃｍ３／ｇであり、平均粒子径が６．３μｍであった。 And after drying the slurry obtained by the ball mill, after baking at 1000 degreeC in air | atmosphere like the comparative example 1, after carrying out a ball mill grinding | pulverization for 24 hours and drying, mixed oxidation of NiO and stabilized zirconia 105 g of product was obtained. This mixed oxide had a pore volume of 0.01 cm 3 / g and an average particle size of 6.3 μm.
比較例３
液温を３０℃に設定して、実施例１と同様に炭酸水素ナトリウム粉末を少量ずつ添加し、沈殿物を生成させた。ＣＯ２ガスの発泡が起こらなくなった時点で、炭酸水素ナトリウム水溶液の添加を終了した。そして、攪拌を中止して、静置させ、沈殿物を沈降させた。
Comparative Example 3
The liquid temperature was set to 30 ° C., and sodium bicarbonate powder was added little by little in the same manner as in Example 1 to produce a precipitate. The addition of the aqueous sodium hydrogen carbonate solution was terminated when no CO 2 gas bubbling occurred. And stirring was stopped, it was left still and the deposit was settled.
この沈殿物を含むスラリーをデカンテーション法により数回洗浄させ、未溶解の炭酸水素ナトリウムと溶解したＮａイオンを除去した。その後、ヌッチェにて吸引ろ過を行い沈殿物と分別した。このとき得られた水分を含んだ沈殿物は１４１０ｇであった。 The slurry containing the precipitate was washed several times by a decantation method to remove undissolved sodium bicarbonate and dissolved Na ions. Thereafter, suction filtration was performed with Nutsche to separate from precipitates. The water-containing precipitate obtained at this time was 1410 g.
得られた沈殿物を大気中１０００℃にて焼成した後、ＹＳＺボール、イオン交換水とともにポリエチレン製ポットに入れ、２４時間ボールミル粉砕した後、乾燥させることにより、ＮｉＯと安定化ジルコニアとの混合酸化物８５ｇを得た。この混合酸化物は、細孔容積０．０８ｃｍ３／ｇであり、平均粒子径が０．４５μｍであった。 After firing the resulting precipitate at 1000 ° C. in the atmosphere, it is put in a polyethylene pot together with YSZ balls and ion-exchanged water, ball milled for 24 hours, and then dried to mix and oxidize NiO and stabilized zirconia. 85 g of product was obtained. This mixed oxide had a pore volume of 0.08 cm 3 / g and an average particle size of 0.45 μm.
試験例１
１）ＳＯＦＣセルの気孔率
次に、各実施例及び比較例で得られた各ＮｉＯと安定化ジルコニアの混合酸化物２７ｇと、エタノール６８ｇ、分散剤としてポリカルボン酸型高分子界面活性剤１ｇ、消泡剤としてジアルキルスルホコハク酸塩１ｇ、バインダーとしてセルロース３ｇを混合し、スラリーを得た。このスラリーを予め焼結させたＳｃＳＺ基板上にディッピングによりスラリーコートをした。これを乾燥後、１３００℃にて焼成し、アノード膜を得た。得られた膜は約８０ミクロンであった。気孔率の結果も表１に示す。この結果では、実施例１〜３、すなわち化学反応により炭酸ガスを発生させながら得られた混合粉ほうが気孔率が大きく、比較例で示した通常の方法より１．４〜２．６倍大きくなった。
Test example 1
1) Porosity of SOFC cell Next, 27 g of each mixed oxide of NiO and stabilized zirconia obtained in each Example and Comparative Example, 68 g of ethanol, 1 g of a polycarboxylic acid type polymer surfactant as a dispersant, 1 g of dialkyl sulfosuccinate as an antifoaming agent and 3 g of cellulose as a binder were mixed to obtain a slurry. Slurry coating was performed by dipping on a pre-sintered ScSZ substrate. This was dried and fired at 1300 ° C. to obtain an anode film. The resulting film was approximately 80 microns. The porosity results are also shown in Table 1. In this result, Examples 1-3, that is, the mixed powder obtained while generating carbon dioxide by chemical reaction has a large porosity, which is 1.4 to 2.6 times larger than the usual method shown in the comparative example. It was.
２）アノード膜の導電率測定
次に、作製したアノード膜を水素ガス雰囲気中１０００℃で５時間かけて還元した後、四端子法により導電率を測定した。その結果を表１に示す。この結果では、実施例１の条件のＮｉＯと安定化ジルコニアの混合酸化物が最も高い導電率（２，０３０ Ｓ／ｃｍ）を示した。比較例１で示した従来の固体混合法による原料粉末を用いた膜では、導電率は１，７００Ｓ／ｃｍ近辺であることから、実施例１では導電率が約２０％向上した。
2) Measurement of conductivity of anode film Next, the produced anode film was reduced in a hydrogen gas atmosphere at 1000 ° C for 5 hours, and then the conductivity was measured by a four-terminal method. The results are shown in Table 1. As a result, the mixed oxide of NiO and stabilized zirconia under the conditions of Example 1 showed the highest conductivity (2,030 S / cm). In the film using the raw material powder by the conventional solid mixing method shown in Comparative Example 1, the conductivity is around 1,700 S / cm, and therefore, in Example 1, the conductivity was improved by about 20%.
３）発電評価
各実施例及び比較例で作製したＮｉＯと安定化ジルコニアの混合酸化物を使用して発電試験セルを作製して評価した。まず、気孔率測定と同様にスラリーを作製した。また、第一稀元素化学工業（株）製空気極（ＬａＳｒＭｎＯ３）でも気孔率測定時と同様な方法でスラリーを作製した。これを第一稀元素化学工業（株）製のスカンジア安定化ジルコニア１０Ｓｃ１ＣｅＳＺを用いた厚さ２００μｍの電解質基板に塗布し、乾燥した後、大気中１４００℃で焼成し、さらに３％水素ガス雰囲気中１０００℃にて還元処理をした。燃料；１１％Ｈ２Ｏ、８９％Ｈ２、酸化剤；空気４倍等量、燃料利用率４０％、温度１０００℃の運転条件で発電評価した。その結果を表１に示す。この結果、実施例１で調製したＮｉＯと安定化ジルコニアの混合酸化物を用いたセルで最大出力０．９７Ｗ／ｃｍ２の高出力を示し、比較例で示した従来の粉末混合による粉末を用いて作製したセルの最大出力（約０．４５Ｗ／ｃｍ２）より高いことが確認された。
3) Power generation evaluation A power generation test cell was prepared and evaluated using the mixed oxide of NiO and stabilized zirconia prepared in each of the examples and comparative examples. First, a slurry was prepared in the same manner as the porosity measurement. Further, to prepare a slurry Daiichi Kigenso Kagaku Kogyo Co., Ltd. air electrode (LaSrMnO 3) same as when the porosity measured in Method. This was applied to an electrolyte substrate having a thickness of 200 μm using scandia-stabilized zirconia 10Sc1CeSZ manufactured by Daiichi Rare Element Chemical Co., Ltd., dried, fired at 1400 ° C. in the atmosphere, and further in a 3% hydrogen gas atmosphere. Reduction treatment was performed at 1000 ° C. Fuel generation: 11% H 2 O, 89% H 2 , oxidizing agent: air equivalent to 4 times, fuel utilization rate 40%, temperature 1000 ° C. The results are shown in Table 1. As a result, the cell using the mixed oxide of NiO and stabilized zirconia prepared in Example 1 showed a high output of a maximum output of 0.97 W / cm 2 , and the conventional powder mixed powder shown in the comparative example was used. It was confirmed that it was higher than the maximum output (about 0.45 W / cm 2 ) of the manufactured cell.
Claims (6)
（１）前記材料は、第１成分として酸化ニッケル、第２成分として酸化ジルコニウム、ならびに第３成分として酸化スカンジウム、酸化イットリウム及び酸化カルシウムの少なくとも１種を含む組成を有し、
（２）前記材料は、細孔容積０．１〜１．５ｃｍ３／ｇの粉末である、
ことを特徴とする固体酸化物型燃料電池の燃料極用材料。 An electrode material for use in a fuel electrode of a solid oxide fuel cell,
(1) The material has a composition containing nickel oxide as a first component, zirconium oxide as a second component, and at least one of scandium oxide, yttrium oxide, and calcium oxide as a third component,
(2) The material is a powder having a pore volume of 0.1 to 1.5 cm 3 / g.
A material for a fuel electrode of a solid oxide fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007138884A JP5191166B2 (en) | 2007-05-25 | 2007-05-25 | Material for anode of solid oxide fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007138884A JP5191166B2 (en) | 2007-05-25 | 2007-05-25 | Material for anode of solid oxide fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008293828A JP2008293828A (en) | 2008-12-04 |
| JP5191166B2 true JP5191166B2 (en) | 2013-04-24 |
Family
ID=40168349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007138884A Active JP5191166B2 (en) | 2007-05-25 | 2007-05-25 | Material for anode of solid oxide fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5191166B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011190148A (en) * | 2010-03-15 | 2011-09-29 | Sumitomo Osaka Cement Co Ltd | Composite ceramic powder and method for producing the same, and solid oxide fuel cell |
| JP2011190149A (en) * | 2010-03-15 | 2011-09-29 | Sumitomo Osaka Cement Co Ltd | Composite ceramic powder and method for producing the same, and solid oxide fuel cell |
| US20120251922A1 (en) * | 2011-03-28 | 2012-10-04 | WATT Fuel Cell Corp | Electrode for a solid oxide fuel cell and method for its manufacture |
| US10483578B2 (en) | 2013-10-02 | 2019-11-19 | Lg Chem, Ltd. | Method for manufacturing anode support of solid oxide fuel cell, and anode support of solid oxide fuel cell |
| US10615420B2 (en) | 2015-09-18 | 2020-04-07 | Lg Chem, Ltd. | Electrode slurry of solid oxide fuel cell, green sheet for electrode of solid oxide fuel cell, electrode of solid oxide fuel cell, and method for manufacturing solid oxide fuel cell and electrode of solid oxide fuel cell |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3604210B2 (en) * | 1995-09-20 | 2004-12-22 | 九州電力株式会社 | Method for producing NiO / YSZ composite powder |
| JP4171334B2 (en) * | 2003-03-25 | 2008-10-22 | 株式会社日本触媒 | Anode support substrate for solid oxide fuel cell and process for producing the same |
| JP2006012764A (en) * | 2004-05-28 | 2006-01-12 | Dowa Mining Co Ltd | Material for electrode of solid electrolyte type fuel cell and electrode |
-
2007
- 2007-05-25 JP JP2007138884A patent/JP5191166B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008293828A (en) | 2008-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5689107B2 (en) | Manufacturing method of NiO-ceramic composite powder and NiO-ceramic composite fuel electrode | |
| JP4037899B2 (en) | Powdered metal oxide mother particles, powdered metal oxide child particles, method for producing powdered metal oxide particles, powdered composite particles, and electrode for solid oxide fuel cell | |
| JP2009016350A (en) | Electrode/electrolyte composite powder for fuel cell, and its preparation method | |
| Accardo et al. | Gadolinium-doped ceria nanopowders synthesized by urea-based homogeneous co-precipitation (UBHP) | |
| AU2008325771B2 (en) | Nickel oxide powder material for solid oxide fuel cell, process for producing the nickel oxide powder material, and fuel electrode material, fuel electrode, and solid oxide fuel cell using the nickel oxide powder material | |
| JP5191166B2 (en) | Material for anode of solid oxide fuel cell | |
| JP5439959B2 (en) | Electrode for solid oxide fuel cell and cell for solid oxide fuel cell | |
| KR101587305B1 (en) | Nickel oxide-stabilized zirconia composite oxide, process for production thereof, and anode for solid oxide type fuel cell comprising the composite oxide | |
| JP5617717B2 (en) | Composite ceramic material, method for producing the same, and solid oxide fuel cell | |
| JP2010251141A (en) | Composite nickel oxide powder material for solid oxide fuel cell and method of manufacturing the same, and fuel electrode material using the same | |
| JP5175154B2 (en) | Production method of nickel composite oxide, nickel composite oxide obtained by the method, nickel oxide-stabilized zirconia composite oxide using the nickel composite oxide, and nickel oxide-stabilized zirconia composite oxide Fuel electrode for solid oxide fuel cell | |
| JP2010282933A (en) | Air electrode for solid oxide fuel cell, and cell of solid oxide fuel cell | |
| JP5401847B2 (en) | Composite ceramic powder, method for producing the same, and solid oxide fuel cell | |
| JP2007115536A (en) | Manufacturing method of electrode for porous solid oxide fuel cell | |
| JP2008541359A (en) | Fuel cell cathode with large surface area | |
| JP2006244810A (en) | Electrode for solid oxide fuel cell and its manufacturing method | |
| CN106953111B (en) | A kind of preparation method of samarium doping cerium oxide solid electrolyte powder | |
| US20140038069A1 (en) | Barium cerate nanoparticles for use in solid oxide fuel cells | |
| JP2018063871A (en) | Fuel electrode for electrochemical cell, and electrochemical cell including the same | |
| JP5516468B2 (en) | Composite ceramic material, method for producing the same, and solid oxide fuel cell | |
| Majee et al. | Strategies to Develop Electrocatalytically Active Perovskite Oxide Nanosheets | |
| JP6779745B2 (en) | Solid oxide fuel cell and material for forming the cathode of the fuel cell | |
| JP6318877B2 (en) | Composite ceramic material and method for producing the same, slurry for solid oxide fuel cell, fuel electrode for solid oxide fuel cell, and solid oxide fuel cell | |
| KR101787811B1 (en) | Method of manufacturing electrode, electrode manufactured by the method and fuel cell comprising the same | |
| JP7477729B2 (en) | Composite oxide powder and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100312 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120807 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120814 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121003 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130108 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130129 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5191166 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160208 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |