JP6813855B2 - 複合粒子粉末、固体酸化物形セル用電極材及びそれを用いた固体酸化物形セル用電極 - Google Patents
複合粒子粉末、固体酸化物形セル用電極材及びそれを用いた固体酸化物形セル用電極 Download PDFInfo
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- JP6813855B2 JP6813855B2 JP2018549093A JP2018549093A JP6813855B2 JP 6813855 B2 JP6813855 B2 JP 6813855B2 JP 2018549093 A JP2018549093 A JP 2018549093A JP 2018549093 A JP2018549093 A JP 2018549093A JP 6813855 B2 JP6813855 B2 JP 6813855B2
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- 239000011246 composite particle Substances 0.000 title claims description 144
- 239000000843 powder Substances 0.000 title claims description 137
- 239000007787 solid Substances 0.000 title claims description 64
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- 239000004020 conductor Substances 0.000 claims description 100
- 239000000446 fuel Substances 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 51
- 239000003792 electrolyte Substances 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
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- 238000005259 measurement Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- 229910052772 Samarium Inorganic materials 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 description 68
- 229910052751 metal Inorganic materials 0.000 description 45
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 19
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- 238000000034 method Methods 0.000 description 14
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- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 10
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
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- MDQGGVWCQUPBRU-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.O.O.[Ce] Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Ce] MDQGGVWCQUPBRU-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- FLHWBWDRXIOUBB-UHFFFAOYSA-N cerium hexahydrate Chemical compound O.O.O.O.O.O.[Ce] FLHWBWDRXIOUBB-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
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- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
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- 229910002076 stabilized zirconia Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021523 barium zirconate Inorganic materials 0.000 description 4
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910003321 CoFe Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000003764 ultrasonic spray pyrolysis Methods 0.000 description 3
- -1 (LaSr) MnO 3 Chemical class 0.000 description 2
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 2
- 229910002484 Ce0.9Gd0.1O1.95 Inorganic materials 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 241000968352 Scandia <hydrozoan> Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
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- 238000000691 measurement method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing 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
- 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 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910002148 La0.6Sr0.4MnO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DSJYSRTZHXBOCX-UHFFFAOYSA-N ac1l9i4c Chemical compound O.O.O.O DSJYSRTZHXBOCX-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910002086 ceria-stabilized zirconia Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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Description
該電子伝導性材料が、下記一般式(1):
A (1−x) B (x) C (y) O 3 (1)
(一般式(1)中、AはY、La、Ce、Pr、Sm及びGdのうちの1種以上である。BはSr、Ca及びBaのうちの1種以上である。CはCr、Mn、Fe、Co、Ni及びCuのうちの1種以上である。xは0.2〜0.5である。yは1.0〜1.15である。)
で表され、Cサイトに少なくともCoを含有しているペロブスカイト型酸化物材料であり、
該複合粒子粉末の粒度分布測定における体積基準の50%粒径(D50)が0.1〜2.0μmであり、
該複合粒子粉末の粒度分布測定における体積基準の25%粒径(D25)に対する75%粒径(D75)の比(D75/D25)が1.1〜2.2であり、
該複合粒子粉末のD50とBET比表面積が下記:
(I)0.1μm≦前記複合粒子粉末のD50≦0.5μmであり且つ前記複合粒子粉末のBET比表面積が20m2/gより大きく200m2/g以下である、
(II)0.5μm<前記複合粒子粉末のD50≦0.9μmであり且つ前記複合粒子粉末のBET比表面積が4m2/gより大きく50m2/g以下である、
(III)0.9μm<前記複合粒子粉末のD50≦1.3μmであり且つ前記複合粒子粉末のBET比表面積が2.5m2/gより大きく30m2/g以下である、
(IV)1.3μm<前記複合粒子粉末のD50≦2.0μmであり且つ前記複合粒子粉末のBET比表面積が2m2/gより大きく20m2/g以下であること、
のいずれかを満たし、該複合粒子粉末中の該イオン伝導性材料の含有率が、35〜75質量%であること、
を特徴とする複合粒子粉末。
(2)(1)記載の複合粒子粉末を、成形及び焼成して得られる固体酸化物形セル用電極。
(3)前期複合粒子粉末が、空気極用の複合粒子粉末であることを特徴とする(2)記載の固体酸化物形セル用電極。
(4)前期複合粒子粉末が、燃料極用の複合粒子粉末であることを特徴とする(2)記載の固体酸化物形セル用電極。
(5)電解質と、該電解質を挟み込む空気極と燃料極から構成され、該空気極が、(3)記載の固体酸化物形セル用電極であることを特徴とする固体酸化物形セル。
(6)電解質と、該電解質を挟み込む空気極と燃料極から構成され、該空気極が、(4)記載の固体酸化物形セル用電極であることを特徴とする固体酸化物形セル。
該複合粒子粉末の粒度分布測定における体積基準の50%粒径(D50)が0.1〜2.0μmであり、
該複合粒子粉末の粒度分布測定における体積基準の25%粒径(D25)に対する75%粒径(D75)の比(D75/D25)が1.1〜2.2であり、
該複合粒子粉末のD50とBET比表面積が下記:
(I)0.1μm≦前記複合粒子粉末のD50≦0.5μmの場合、前記複合粒子粉末のBET比表面積が20m2/gより大きく200m2/g以下であり、
(II)0.5μm<前記複合粒子粉末のD50≦0.9μmの場合、前記複合粒子粉末のBET比表面積が4m2/gより大きく50m2/g以下であり、
(III)0.9μm<前記複合粒子粉末のD50≦1.3μmの場合、前記複合粒子粉末のBET比表面積が2.5m2/gより大きく30m2/g以下であり、
(IV)1.3μm<前記複合粒子粉末のD50≦2.0μmの場合、前記複合粒子粉末のBET比表面積が2m2/gより大きく20m2/g以下であること、
を満たし、該複合粒子粉末中の該イオン伝導性材料の含有率が、35〜75質量%であること、
を特徴とする複合粒子粉末である。
なお、本明細書において、数値範囲を「〜」を用いて示す時、両端の数値を含む。
A(1−x)B(x)C(y)O3 (1)
で表されるペロブスカイト型酸化物材料が好ましい。
(I)0.1μm≦複合粒子粉末のD50≦0.5μmの場合、複合粒子粉末のBET比表面積は、20m2/gより大きく200m2/g以下、好ましくは25〜150m2/g、特に好ましくは30〜120m2/gである。
(II)0.5μm<複合粒子粉末のD50≦0.9μmの場合、複合粒子粉末のBET比表面積は、4m2/gより大きく50m2/g以下、好ましくは5〜40m2/g、特に好ましくは6〜30m2/gである。
(III)0.9μm<複合粒子粉末のD50≦1.3μmの場合、複合粒子粉末のBET比表面積は、2.5m2/gより大きく30m2/g以下、好ましくは3〜25m2/g、特に好ましくは4〜20m2/gである。
(IV)1.3μm<複合粒子粉末のD50≦2.0μmの場合、複合粒子粉末のBET比表面積は、2m2gより大きく20m2/g以下、好ましくは2.5〜18m2/g、特に好ましくは3〜15m2/gである。
(1)噴霧用水溶液s1
硝酸サマリウム六水和物16.07g、硝酸ストロンチウム5.70g、硝酸コバルト六水和物15.67g及び硝酸セリウム六水和物16.04gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s1を調製した。該噴霧用水溶液s1を噴霧熱分解することにより、1Lあたり0.1molの60質量%Sm0.5Sr0.5Co3(以下、SSC)−40質量%Ce0.8Sm0.2O1.9(以下、SDC)を合成できる。
(2)噴霧用水溶液s2
硝酸サマリウム六水和物14.72g、硝酸ストロンチウム4.63g、硝酸コバルト六水和物12.73g及び硝酸セリウム六水和物19.54gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s2を調製した。該噴霧用水溶液s2を噴霧熱分解することにより、1Lあたり0.1molの50質量%SSC−50質量%SDCを合成できる。
(3)噴霧用水溶液s3
硝酸サマリウム六水和物13.44g、硝酸ストロンチウム3.61g、硝酸コバルト六水和物9.94g及び硝酸セリウム六水和物22.88gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s3を調製した。該噴霧用水溶液s3を噴霧熱分解することにより、1Lあたり0.1molの40質量%SSC−60質量%SDCを合成できる。
(4)噴霧用水溶液s4
硝酸サマリウム六水和物12.22g、硝酸ストロンチウム2.64g、硝酸コバルト六水和物7.27g及び硝酸セリウム六水和物26.06gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s4を調製した。該噴霧用水溶液s4を噴霧熱分解することにより、1Lあたり0.1molの30質量%SSC−70質量%SDCを合成できる。
(5)噴霧用水溶液s5
硝酸サマリウム六水和物11.63g、硝酸ストロンチウム2.18g、硝酸コバルト六水和物5.99g及び硝酸セリウム六水和物27.59gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s5を調製した。該噴霧用水溶液s5を噴霧熱分解することにより、1Lあたり0.1molの25質量%SSC−75質量%SDCを合成できる。
(6)噴霧用水溶液s6
硝酸ランタン六水和物8.50g、硝酸ストロンチウム2.77g、硝酸マンガン六水和物9.39g、硝酸ジルコニル二水和物16.55g及び硝酸イットリウム六水和物4.12gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s6を調製した。該噴霧用水溶液s6を噴霧熱分解することにより、1Lあたり0.1molの45質量%La0.6Sr0.4MnO3(以下、LSM)−55質量%(ZrO2)0.92(Y2O3)0.08(以下、8YSZ)を合成できる。
(1)噴霧用水溶液s7
硝酸サマリウム六水和物18.98g、硝酸ストロンチウム8.01g、硝酸コバルト六水和物22.02g及び硝酸セリウム六水和物8.45gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s7を調製した。該噴霧用水溶液s7を噴霧熱分解することにより、1Lあたり0.1molの80質量%SSC−20質量%SDCを合成できる。
(2)噴霧用水溶液s8
硝酸サマリウム六水和物3.50g、硝酸ストロンチウム1.36g、硝酸コバルト六水和物3.75g及び硝酸セリウム六水和物2.47gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s8を調製した。該噴霧用水溶液s8を噴霧熱分解することにより、1Lあたり0.02molの70質量%SSC−30質量%SDCを合成できる。
(3)噴霧用水溶液s9
硝酸サマリウム六水和物17.49g、硝酸ストロンチウム6.82g、硝酸コバルト六水和物18.76g及び硝酸セリウム六水和物12.34gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s9を調製した。該噴霧用水溶液s9を噴霧熱分解することにより、1Lあたり0.1molの70質量%SSC−30質量%SDCを合成できる。
(4)噴霧用水溶液s10
硝酸サマリウム六水和物87.43g、硝酸ストロンチウム34.11g、硝酸コバルト六水和物93.81g及び硝酸セリウム六水和物61.72gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s10を調製した。該噴霧用水溶液s10を噴霧熱分解することにより、1Lあたり0.5molの70質量%SSC−30質量%SDCを合成できる。
(5)噴霧用水溶液s11
硝酸サマリウム六水和物11.06g、硝酸ストロンチウム1.72g、硝酸コバルト六水和物4.74g及び硝酸セリウム六水和物29.08gを秤量し、純水に溶解させ、次いで、水溶液量が1000mlになるようにさらに純水を加え、噴霧用水溶液s11を調製した。該噴霧用水溶液s11を噴霧熱分解することにより、1Lあたり0.1molの20質量%SSC−80質量%SDCを合成できる。
実施例1〜6及び比較例1〜5では、前記噴霧用水溶液s1〜s6及びs7〜s11を用いて、超音波方式の噴霧熱分解法により、噴霧熱分解を行い、10種のSSC−SDCの複合粒子粉末と1種のLSM−8YSZの複合粒子粉末を得た。なお、キャリアーガスとしては、空気を用い、加熱炉としては、3段式電気炉(炉内温度は前段から300、700、900℃、炉内加熱時間は前段から8秒、8秒、8秒)を用いた。
比較例6では、市販品のSSC(D50=0.9μm、日下レアメタル研究所製)、及び市販品のSDC(D50=0.1μm、北興化学工業製)を用意し、表1に示す割合で混合した。
得られた複合粒子粉末の粒度分布を、ヘキサメタリン酸ナトリウム水溶液(0.2質量%)に分散させ、レーザー回折式粒度分布測定法(日機装株式会社製、マイクロトラックHRA9320−X100)により1回あたり30秒を3回測定し、その平均値より、体積基準のD25、D50及びD75と、D75/D25の値を求めた。その結果を表1に示す。
得られた複合粒子粉末のBET比表面積を、高精度・多検体ガス吸着量測定装置(カンタクローム・インスツルメンツ・ジャパン合同会社製、AutosorbーiQ)を用いて窒素吸着BET5点法で測定した。その結果を表1に示す。
得られた複合粒子粉末の質量比を、XRD回折結果をリートベルト解析することによって求めた。その結果を表1に示す。
上記のようにして得られた複合粒子粉末100質量%に対して、エチルセルロースを8質量%、可塑剤を8質量%、分散剤を4.8質量%、α−テレピネオール60質量%混合したものを、混錬器にて、室温で1分30秒間混錬することにより、電極用スラリーを得た。次いで、該電極用スラリーを、スクリーン印刷法にて、膜厚が20μmとなるように、SSC−SDC(実施例1〜5及び比較例1〜6)はCe0.9Gd0.1O1.95焼結体ペレット上に、LSM−8YSZ(実施例6)は8YSZ焼結体ペレット上に成形した。なお、前記Ce0.9Gd0.1O1.95焼結体ペレットは、Ce0.9Gd0.1O1.95粉末(CGO90/10、UHSA、ソルベイ・スペシャルケム・ジャパン製)2.2gを、26mm径の超硬ダイスを使用し20MPaで一軸プレス成形した後、1350℃で3時間で焼成することで得た。また、前記8YSZ焼結体ペレットは、8YSZ粉末(TZ−8Y、東ソー製)1.5gを、26mm径の超硬ダイスを使用し20MPaで一軸プレス成形した後、1350℃で3時間で焼成することで得た。次いで、SSC−SDC(実施例1〜5及び比較例1〜6)は950℃で1時間、LSM−8YSZ(実施例6)は1200℃で3時間焼成することで、電極を製造した。
得られた電極について、交流インピーダンス法(1287、1255B、ソーラトロン製)により、空気雰囲気下、800℃における面積あたりの電極抵抗を測定した。その結果を表1に示す。なお、電極抵抗とは、交流インピーダンス法より得られる測定対象のセルのコール・コール・プロット、すなわち、周波数を変化させた時の周波数毎の実数部抵抗値Z’(Ω)及び虚数部抵抗値Z”(Ω)を、横軸を実数部抵抗値Z’、縦軸を虚数部抵抗値Z”として、プロットして得られるグラフにおいて、該グラフの横軸との2つの切片の実数部抵抗値の差である。
2)10Sc1CeSZ:酸化物換算で10mol%のスカンジア及び1mol%のセリアを含有するスカンジアセリア安定化ジルコニア
3)800℃における電極抵抗
4)参考例1〜4は、特許文献(特開2010−282932号公報)中の表1の値を引用
Claims (6)
- 電子伝導性材料及びイオン伝導性材料が凝集した複合粒子粉末であり、
該電子伝導性材料が、下記一般式(1):
A (1−x) B (x) C (y) O 3 (1)
(一般式(1)中、AはY、La、Ce、Pr、Sm及びGdのうちの1種以上である。BはSr、Ca及びBaのうちの1種以上である。CはCr、Mn、Fe、Co、Ni及びCuのうちの1種以上である。xは0.2〜0.5である。yは1.0〜1.15である。)
で表され、Cサイトに少なくともCoを含有しているペロブスカイト型酸化物材料であり、
該複合粒子粉末の粒度分布測定における体積基準の50%粒径(D50)が0.1〜2.0μmであり、
該複合粒子粉末の粒度分布測定における体積基準の25%粒径(D25)に対する75%粒径(D75)の比(D75/D25)が1.1〜2.2であり、
該複合粒子粉末のD50とBET比表面積が下記:
(I)0.1μm≦前記複合粒子粉末のD50≦0.5μmであり且つ前記複合粒子粉末のBET比表面積が20m2/gより大きく200m2/g以下である、
(II)0.5μm<前記複合粒子粉末のD50≦0.9μmであり且つ前記複合粒子粉末のBET比表面積が4m2/gより大きく50m2/g以下である、
(III)0.9μm<前記複合粒子粉末のD50≦1.3μmであり且つ前記複合粒子粉末のBET比表面積が2.5m2/gより大きく30m2/g以下である、
(IV)1.3μm<前記複合粒子粉末のD50≦2.0μmであり且つ前記複合粒子粉末のBET比表面積が2m2/gより大きく20m2/g以下であること、
のいずれかを満たし、該複合粒子粉末中の該イオン伝導性材料の含有率が、35〜75質量%であること、
を特徴とする複合粒子粉末。 - 請求項1記載の複合粒子粉末を、成形及び焼成して得られる固体酸化物形セル用電極。
- 前記複合粒子粉末が、空気極用の複合粒子粉末であることを特徴とする請求項2記載の固体酸化物形セル用電極。
- 前記複合粒子粉末が、燃料極用の複合粒子粉末であることを特徴とする請求項2記載の固体酸化物形セル用電極。
- 電解質と、該電解質を挟み込む空気極と燃料極から構成され、該空気極が、請求項3記載の固体酸化物形セル用電極であることを特徴とする固体酸化物形セル。
- 電解質と、該電解質を挟み込む空気極と燃料極から構成され、該燃料極が、請求項4記載の固体酸化物形セル用電極であることを特徴とする固体酸化物形セル。
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