JP6293418B2 - Electrode for solid oxide fuel cell and solid oxide fuel cell - Google Patents
Electrode for solid oxide fuel cell and solid oxide fuel cell Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims description 81
- 239000007787 solid Substances 0.000 title claims description 50
- 239000002245 particle Substances 0.000 claims description 159
- 239000000919 ceramic Substances 0.000 claims description 132
- 239000007784 solid electrolyte Substances 0.000 claims description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052863 mullite Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 4
- 229910052845 zircon Inorganic materials 0.000 claims description 4
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 17
- 238000005245 sintering Methods 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002003 electrode paste Substances 0.000 description 13
- 239000011343 solid material Substances 0.000 description 11
- 239000002737 fuel gas Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- -1 oxygen ion Chemical class 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229960004559 theobromine Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 239000012508 resin bead Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229910002080 8 mol% Y2O3 fully stabilized ZrO2 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- 239000005977 Ethylene Substances 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 229910018245 LaO Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910002078 fully stabilized zirconia Inorganic materials 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Description
本発明は、例えば固体電解質型燃料電池用電極及び固体電解質型燃料電池セルに関する。 The present invention relates to an electrode for a solid oxide fuel cell and a solid oxide fuel cell, for example.
従来より、燃料電池として、固体電解質（固体酸化物）を用いた固体酸化物燃料電池（以下ＳＯＦＣとも記す）が知られている。
このＳＯＦＣは、例えば板状の固体電解質体の各面に燃料極と空気極とを備えた燃料電池セルを、多数積層してスタックを形成し、燃料極に燃料ガスを供給するとともに、空気極に空気を供給し、燃料（例えば水素）と空気中の酸素とを固体電解質体を介して化学反応させることによって電力を発生させるものである。
上記した燃料極に用いられる電極として、水素への活性が高い遷移金属粒子（Ｎｉ，Ｃｏ，Ｒｕ，Ｆｅ，Ｃｕ）と固体電解質セラミックス粒子（Ｚｒ系電解質体やＣｅ系電解質体等）とを含む電極ペーストに消失性固体材料（テオブロミン、カーボン、樹脂ビーズ）を混合し、該ペーストを焼結して多数の気孔を形成した多孔質電極が一般に用いられている（特許文献１参照）。多孔質電極とすることで、電極と、固体電解質体と、空気（被測定ガス）とで構成される３相界面の量を増やし、過電圧を低減することができる。
Conventionally, a solid oxide fuel cell (hereinafter also referred to as SOFC) using a solid electrolyte (solid oxide) is known as a fuel cell.
In this SOFC, for example, a large number of fuel cells each provided with a fuel electrode and an air electrode on each surface of a plate-shaped solid electrolyte body are stacked to form a stack, and a fuel gas is supplied to the fuel electrode, and an air electrode is provided. Is supplied with air, and a fuel (for example, hydrogen) and oxygen in the air are chemically reacted through a solid electrolyte body to generate electric power.
As an electrode used for the above-mentioned fuel electrode, transition metal particles (Ni, Co, Ru, Fe, Cu) having high activity to hydrogen and solid electrolyte ceramic particles (Zr-based electrolyte body, Ce-based electrolyte body, etc.) are included. A porous electrode is generally used in which a lossless solid material (theobromine, carbon, resin beads) is mixed with an electrode paste, and the paste is sintered to form a large number of pores (see Patent Document 1). By setting it as a porous electrode, the amount of the three-phase interface comprised by an electrode, a solid electrolyte body, and air (to-be-measured gas) can be increased, and an overvoltage can be reduced.
しかしながら、上記した消失性固体材料を用いて多孔質電極を形成した場合、ペーストに混合される消失性固体材料の粒径制御が難しく、得られる電極の気孔径もばらつくという問題がある。又、消失性固体材料は６００〜８００℃で消失して空隙を形成するが、その後の最終焼成温度（１０００〜１５００℃程度）に昇温される過程で空隙が一部破壊されるため、やはり最終的な電極の気孔径がばらつくことがある。又、消失性固体材料としてテオブロミン、、カーボン、樹脂ビーズを用いた場合、テオブロミンと溶剤・バインダーとの濡れ性が悪いため、電極ペーストの塗布時のレべリング性（平坦性）が劣り、電極厚みがばらつくという問題がある。そして、これらの問題により電極のガス拡散抵抗が大きくなり、ひいては過電圧の低減が難しくなる。
そこで、本発明は、多孔質電極のガス拡散抵抗を安定して小さくし、過電圧の低減に優れた固体電解質型燃料電池用電極及び固体電解質型燃料電池セルの提供を目的とする。
However, when a porous electrode is formed using the above-described vanishing solid material, it is difficult to control the particle size of the vanishing solid material mixed in the paste, and there is a problem that the pore diameter of the obtained electrode varies. The vanishing solid material disappears at 600 to 800 ° C. to form voids, but the voids are partially destroyed in the process of raising the temperature to the final firing temperature (about 1000 to 1500 ° C.). The final electrode pore size may vary. Also, when theobromine, carbon, and resin beads are used as the disappearing solid material, the wettability between theobromine and the solvent / binder is poor, so the leveling property (flatness) when applying the electrode paste is poor, and the electrode There is a problem that the thickness varies. These problems increase the gas diffusion resistance of the electrode, which makes it difficult to reduce the overvoltage.
Therefore, an object of the present invention is to provide a solid oxide fuel cell electrode and a solid electrolyte fuel cell excellent in reducing the overvoltage by stably reducing the gas diffusion resistance of the porous electrode.
上記課題を解決するため、本発明の固体電解質型燃料電池用電極は、ジルコニアを主体とする固体電解質体の表面に設けられる固体電解質型燃料電池用電極であって、Ｎｉ、Ｃｏ、Ｒｕ、Ｆｅ、Ｃｕの群から選ばれる１種以上の金属又はその合金の粒子と、安定化ジルコニア、部分安定化ジルコニア、セリアの中から選ばれる第１セラミックス粒子と、Ａｌ２Ｏ３、ＭｇＯ、Ｌａ２Ｏ３、スピネル、ジルコン、ムライト及びコージェライトの群から選ばれる１種以上の第２セラミックス粒子と、からなり、前記第２セラミックス粒子は、前記第１セラミックス粒子よりも含有量が少ないことを特徴とする。
この固体電解質型燃料電池用電極によれば、電極の焼結時に第１セラミックス粒子に接した第２セラミックス粒子が粒界に析出し、第１セラミックス粒子の粒成長を抑制する。その結果、焼結が進んでも、第１セラミックス粒子と主成分である金属又はその合金の粒子との間の接触点が失われ難くなり、気孔（３相界面）が減少せずにガス拡散抵抗を低減することができる。又、消失性固体材料を用いずに気孔を形成するので、気孔の径や分布がばらつかず、ガス拡散抵抗を安定して低減することができる。
さらに、第２セラミックス粒子は焼結によって消失しないので、この点でも電極の気孔の径や分布のばらつきが少なくなる。又、第１セラミックス粒子、第２セラミックス粒子共に溶剤・バインダーとの濡れ性が良いため、分散性が向上し、結果、電極ペーストの塗布時のレべリング性（平坦性）が向上するので、電極厚みのばらつきも少なくなる。ひいては、電極の過電圧の低減につながる。
In order to solve the above-mentioned problems, a solid oxide fuel cell electrode according to the present invention is a solid electrolyte fuel cell electrode provided on the surface of a solid electrolyte body mainly composed of zirconia, and includes Ni, Co, Ru, Fe Particles of one or more metals selected from the group of Cu or alloys thereof, first ceramic particles selected from stabilized zirconia, partially stabilized zirconia, and ceria, Al 2 O 3 , MgO, La 2 O 3 , one or more second ceramic particles selected from the group of spinel, zircon, mullite, and cordierite, wherein the second ceramic particles have a smaller content than the first ceramic particles. To do.
According to this solid oxide fuel cell electrode, the second ceramic particles in contact with the first ceramic particles are precipitated at the grain boundaries during sintering of the electrode, and the grain growth of the first ceramic particles is suppressed. As a result, even if sintering proceeds, the contact points between the first ceramic particles and the main component metal or alloy particles are not easily lost, and the gas diffusion resistance is reduced without decreasing the pores (three-phase interface). Can be reduced. Further, since the pores are formed without using the disappearing solid material, the diameter and distribution of the pores do not vary, and the gas diffusion resistance can be stably reduced.
Furthermore, since the second ceramic particles are not lost by sintering, the variation in the pore diameter and distribution of the electrode is reduced in this respect as well. In addition, since both the first ceramic particles and the second ceramic particles have good wettability with the solvent / binder, the dispersibility is improved. As a result, the leveling property (flatness) at the time of applying the electrode paste is improved. Variation in electrode thickness is also reduced. As a result, the overvoltage of the electrode is reduced.
第１セラミックス粒子に対し、前記第２セラミックス粒子の含有割合が０．１体積％以上５０体積％未満であると、電極の密着性を低下させずにガス拡散抵抗を低減することができる。 When the content ratio of the second ceramic particles is 0.1 volume% or more and less than 50 volume% with respect to the first ceramic particles, gas diffusion resistance can be reduced without reducing the adhesion of the electrodes.
第１セラミックス粒子に対し、前記第２セラミックス粒子の含有割合が３体積％以上４０体積％未満であると、よりガス拡散抵抗を低減することができるため、好ましい。 It is preferable that the content ratio of the second ceramic particles is 3% by volume or more and less than 40% by volume with respect to the first ceramic particles because gas diffusion resistance can be further reduced.
前記第２セラミックス粒子の焼結平均粒子径は、前記第１セラミックス粒子の０．１倍以上１倍以下であると、電極の密着性を低下させずにガス拡散抵抗を低減することができる。 If the sintered average particle diameter of the second ceramic particles is 0.1 to 1 times that of the first ceramic particles, the gas diffusion resistance can be reduced without reducing the adhesion of the electrodes.
前記第１セラミックス粒子が部分安定化ジルコニアからなっていることが好ましい。 The first ceramic particles are preferably made of partially stabilized zirconia.
本発明の固体電解質型燃料電池セルは、固体電解質体と、当該固体電解質体上に設けられる一対の電極と、を少なくとも備えた固体電解質型燃料電池セルであって、前記一対の電極のうち、いずれか一方の電極として、請求項１〜５のいずれかに記載の固体電解質型燃料電池用電極を用いる。 The solid oxide fuel cell of the present invention is a solid electrolyte fuel cell comprising at least a solid electrolyte body and a pair of electrodes provided on the solid electrolyte body, and the As one of the electrodes, the electrode for a solid oxide fuel cell according to any one of claims 1 to 5 is used.
前記固体電解質型燃料電池用電極が、アノード用電極であることがより好ましい。 More preferably, the solid oxide fuel cell electrode is an anode electrode.
又、前記固体電解質型燃料電池用電極の厚みが１〜２０μｍであると、ガス拡散抵抗の低減効果がより大きくなる。 Further, when the thickness of the electrode for the solid oxide fuel cell is 1 to 20 μm, the effect of reducing the gas diffusion resistance is further increased.
この発明によれば、ＳＯＦＣに用いる多孔質電極のガス拡散抵抗を安定して小さくし、過電圧を低減することができる。 According to the present invention, the gas diffusion resistance of the porous electrode used for SOFC can be stably reduced, and the overvoltage can be reduced.
以下、本発明の実施形態の固体電解質型燃料電池を詳細に説明する。
ａ）まず、固体電解質型燃料電池の基本構成である単セル（即ち固体電解質型燃料電池セル）について説明する。
Hereinafter, a solid oxide fuel cell according to an embodiment of the present invention will be described in detail.
a) First, a single cell (that is, a solid oxide fuel cell) that is a basic configuration of a solid oxide fuel cell will be described.
例えば、図１に模式的に示す様に、固体電解質型燃料電池の基本構成である固体電解質型燃料電池セル１では、燃料ガス（例えば水素）に接する燃料極３と、酸素イオン導電性を有する固体電解質体５と、酸化ガス（例えば空気中の酸素）に接触する空気極７とが、この順に積層されている。また、固体電解質体５と空気極７との間には、反応防止層９が形成されている。 For example, as schematically shown in FIG. 1, the solid oxide fuel cell 1 which is a basic configuration of a solid oxide fuel cell has a fuel electrode 3 in contact with a fuel gas (for example, hydrogen) and oxygen ion conductivity. A solid electrolyte body 5 and an air electrode 7 in contact with an oxidizing gas (for example, oxygen in the air) are stacked in this order. A reaction preventing layer 9 is formed between the solid electrolyte body 5 and the air electrode 7.
尚、図１では、燃料極３が支持基体となるいわゆる支持膜式の固体電解質型燃料電池セル１を例に挙げているが、本発明は、固体電解質体が支持基体となる自立膜式の固体電解質型燃料電池セルにも適用することができる。つまり、燃料極、固体電解質体、及び空気極のいずれも支持基体とすることができる。 In FIG. 1, a so-called support membrane type solid electrolyte fuel cell 1 in which the fuel electrode 3 serves as a support base is taken as an example, but the present invention is a self-supporting membrane type in which the solid electrolyte body serves as a support base. It can also be applied to solid oxide fuel cells. That is, any of the fuel electrode, the solid electrolyte body, and the air electrode can be used as the support base.
ｂ）次に、単セルを複数備えた固体電解質型燃料電池のスタック（即ち固体電解質型燃料電池スタック）について説明する。
例えば図２及び図３に示す様に、固体電解質型燃料電池スタック１１は、上述した構成を有する固体電解質型燃料電池セル１が、複数個積層されたものである。
b) Next, a solid oxide fuel cell stack having a plurality of single cells (that is, a solid oxide fuel cell stack) will be described.
For example, as shown in FIGS. 2 and 3, the solid oxide fuel cell stack 11 is formed by stacking a plurality of solid oxide fuel cells 1 having the above-described configuration.
詳しくは、図３に示す様に、固体電解質型燃料電池スタック１１では、固体電解質型燃料電池セル１を主要部とする発電層１３が、金属製のインターコネクター１５を介して、同図の上下方向に複数積層されている。尚、同図では、反応防止層９の記載は省略されている。 Specifically, as shown in FIG. 3, in the solid oxide fuel cell stack 11, the power generation layer 13 mainly composed of the solid oxide fuel cell 1 is connected to the upper and lower sides of the figure via a metal interconnector 15. A plurality of layers are stacked in the direction. In the figure, the description of the reaction preventing layer 9 is omitted.
また、各固体電解質型燃料電池セル１の燃料極３は、燃料極側集電体１７によりインターコネクター１５に電気的に接続されるとともに、各空気極７は、空気極側集電体１９によりろう材２１を介して他のインターコネクター１５（上下方向の端部では蓋体２３及び底体２５）に電気的に接続されている。 The fuel electrode 3 of each solid oxide fuel cell 1 is electrically connected to the interconnector 15 by a fuel electrode side current collector 17, and each air electrode 7 is connected by an air electrode side current collector 19. It is electrically connected to another interconnector 15 (the lid body 23 and the bottom body 25 at the end in the vertical direction) via the brazing material 21.
更に、各発電層１３は、燃料ガスの流路２７と、酸化ガスである空気の流路２９とを隔離するための隔離セパレータ３１を備える。また、それぞれの発電層１３間を電気的に絶縁するため、セラミック等の絶縁体からなる枠体３３が、積層方向の所定部分に配設されている。 Further, each power generation layer 13 includes an isolation separator 31 for isolating the fuel gas flow path 27 and the oxidizing gas air flow path 29. Further, in order to electrically insulate the power generation layers 13 from each other, a frame 33 made of an insulator such as ceramic is disposed at a predetermined portion in the stacking direction.
ｃ）以下、固体電解質型燃料電池スタック１１の各構成について詳細に説明する。
「固体電解質体５」は、ＺｒＯ２、ＢａＣｅＯ３系酸化物、及びＬａＧａＯ３系酸化物のうち、少なくとも一つからなることが好ましい。また、これらのうち、ＺｒＯ２系酸化物を用いた固体電解質が、機械的強度、化学的安定性、高い酸素イオン伝導性をあわせ持つという点において、特に好ましい。
c) Hereinafter, each configuration of the solid oxide fuel cell stack 11 will be described in detail.
The “solid electrolyte body 5” is preferably made of at least one of ZrO 2 , BaCeO 3 -based oxide, and LaGaO 3 -based oxide. Among these, a solid electrolyte using a ZrO 2 oxide is particularly preferable in that it has both mechanical strength, chemical stability, and high oxygen ion conductivity.
この固体電解質体は、固体電解質型燃料電池の動作時に燃料極に導入される燃料ガス又は空気極に導入される酸化ガスのうち一方の少なくとも一部をイオンとして移動させることができるイオン伝導性を有する。どのようなイオンを伝導することができるかは特に限定されないが、イオンとしては、例えば、酸素イオン及び水素イオン等が挙げられる。 This solid electrolyte body has ion conductivity capable of moving at least a part of one of the fuel gas introduced into the fuel electrode or the oxidizing gas introduced into the air electrode during operation of the solid oxide fuel cell as ions. Have. Although what kind of ion can be conducted is not particularly limited, examples of the ion include oxygen ion and hydrogen ion.
尚、この固体電解質体の厚さは電気抵抗と強度とを勘案し、５〜１００μｍ、特に５〜５０μｍ、更には５〜３０μｍとすることができる。
「燃料極３」は、水素源となる燃料ガスと接触し、単セルにおける負電極として機能する。
The thickness of the solid electrolyte body can be set to 5 to 100 μm, particularly 5 to 50 μm, and further 5 to 30 μm in consideration of electric resistance and strength.
The “fuel electrode 3” is in contact with a fuel gas serving as a hydrogen source and functions as a negative electrode in the single cell.
前記燃料極の形成に用いる材料としては、Ｎｉ及びＹＳＺ（イットリア安定化ジルコニア）等が挙げられるが、それらに限定されず、固体電解質型燃料電池の使用条件等により適宜選択することができる。
燃料極を構成する材料については、後述する。
Examples of the material used for forming the fuel electrode include Ni and YSZ (yttria-stabilized zirconia). However, the material is not limited to these, and can be appropriately selected depending on the use conditions of the solid oxide fuel cell.
The material constituting the fuel electrode will be described later.
「空気極７」は、酸素源となる酸化ガスと接触し、単セルにおける正電極として機能する。
この空気極の形成に用いる材料としては、例えば、下記式（１）の化学式で表される組成の材料を採用する。
The “air electrode 7” is in contact with an oxidizing gas serving as an oxygen source and functions as a positive electrode in a single cell.
As a material used for forming the air electrode, for example, a material having a composition represented by the chemical formula of the following formula (1) is adopted.
Ｌａ1-x-yＳｒxＬｎyＣｏzＦｅ1-zＯ3-δ・・・・（１）
（Ｌｎ＝Ｓｍ、Ｇｄ、Ｐｒ、Ｎｄ）
０.２≦ｘ≦０.４、０.０１≦ｙ≦０.２、０.０５≦ｚ≦０.２、ｘ＋ｙ≦０.５
また、この空気極の熱膨張係数としては、１０.０×１０-6〜１３．０×１０-6（１／Ｋ）の範囲の採用が好適である。つまり、この範囲であれば、ジルコニアに代表される固体電解質の熱膨張係数に近い値となるので、熱膨張のマッチングに優れている。
La 1-xy Sr x Ln y CozFe 1-z O 3-δ ···· (1)
(Ln = Sm, Gd, Pr, Nd)
0.2 ≦ x ≦ 0.4, 0.01 ≦ y ≦ 0.2, 0.05 ≦ z ≦ 0.2, x + y ≦ 0.5
Further, the thermal expansion coefficient of the air electrode is preferably in the range of 10.0 × 10 −6 to 13.0 × 10 −6 (1 / K). That is, if it is this range, since it becomes a value close | similar to the thermal expansion coefficient of the solid electrolyte represented by zirconia, it is excellent in the matching of thermal expansion.
「反応防止層９」としては、ＣｅＯ及び希土類元素を主成分とする材料を採用できる。尚、材料全体がＣｅＯ及び希土類元素で構成されていてもよい。この希土類元素としては、Ｓｍ、Ｇｄを採用できる。 As the “reaction prevention layer 9”, a material mainly composed of CeO and rare earth elements can be adopted. In addition, the whole material may be comprised with CeO and rare earth elements. Sm and Gd can be adopted as the rare earth element.
「燃料極側集電体１７」の材質は、金属が好ましく、例えばＮｉ又はＮｉ基合金等により形成することができる。この燃料極側集電体の形態は、弾性があるものが好ましく、多孔体、発泡体及び金属繊維からなるフェルト又はメッシュ等を挙げることができる。 The material of the “fuel electrode side current collector 17” is preferably a metal, and can be formed of, for example, Ni or a Ni-based alloy. The fuel electrode side current collector preferably has elasticity, and examples thereof include felts or meshes made of porous bodies, foams, and metal fibers.
「空気極側集電体１９」の材質は、金属及び導電性セラミックを用いることができる。この金属としては、燃料極側集電体と同様のものを用いることができるが、非弾性の緻密な板状体であってもかまわない。 As the material of the “air electrode side current collector 19”, a metal and a conductive ceramic can be used. As this metal, the same one as the fuel electrode side current collector can be used, but an inelastic dense plate-like body may be used.
空気極側集電体は一面で空気極と接触し、他面でインターコネクターと接触するように設けることができる。また、インターコネクターと接触する面の少なくとも一部において、空気極側集電体及びインターコネクターをろう材等の接合材を用いて接合することができる。 The air electrode side current collector can be provided so as to be in contact with the air electrode on one surface and in contact with the interconnector on the other surface. Further, the air electrode side current collector and the interconnector can be joined using a joining material such as a brazing material on at least a part of the surface in contact with the interconnector.
このような接合材は、空気極側集電体とインターコネクターとを密着させ、安定して接触させ、接触抵抗が増大することを防止することができる限り特に限定されない。
尚、固体電解質型燃料電池では、空気極側集電体とインターコネクターとの間等、同様に接合材等により気密にシールする必要のある部分が多くあり、これらの接合操作の際に同時に接合することができる。また、ガラス接合でも良いし、コンプレッションシールでも良い。
Such a bonding material is not particularly limited as long as the air electrode side current collector and the interconnector can be brought into close contact with each other and stably contacted to prevent an increase in contact resistance.
In solid oxide fuel cells, there are many parts that need to be hermetically sealed with a bonding material or the like, such as between the air electrode side current collector and the interconnector. can do. Moreover, glass bonding may be used, and a compression seal may be used.
更に、これらの集電体は１種の材料のみからなっていてもよく、２種以上の材料からなっていてもよい。また、異なる材料からなるブロックの集合体であってもよい。
「隔離セパレータ３１」は、発電層に供給する燃料ガス及び酸化ガスが混合しないように隔離するための平板状のセパレータである。この材質としては、金属、特に、ステンレス鋼、ニッケル基合金、クロム基合金等の耐熱合金が挙げられる。
Furthermore, these current collectors may consist of only one type of material, or may consist of two or more types of materials. Moreover, the aggregate | assembly of the block which consists of a different material may be sufficient.
The “isolation separator 31” is a flat separator for isolating fuel gas and oxidant gas supplied to the power generation layer so as not to mix. Examples of the material include metals, particularly heat-resistant alloys such as stainless steel, nickel-base alloys, and chromium-base alloys.
「インターコネクター１５」の材質としては、金属、特に、ステンレス鋼、ニッケル基合金、クロム基合金等の耐熱合金が挙げられる。このうち、クロム基合金は、高い電子伝導性を有しているので好適である。 Examples of the material of the “interconnector 15” include metals, particularly heat-resistant alloys such as stainless steel, nickel-base alloys, and chromium-base alloys. Of these, chromium-based alloys are preferred because they have high electronic conductivity.
「燃料ガス」は、水素、水素源となる炭化水素、水素と炭化水素との混合ガス、及びこれらのガスを所定温度の水中を通過させ加湿した燃料ガス、これらのガスに水蒸気を混合させた燃料ガス等が挙げられる。 “Fuel gas” includes hydrogen, hydrocarbon as a hydrogen source, mixed gas of hydrogen and hydrocarbon, fuel gas obtained by passing these gases through water at a predetermined temperature and humidifying them, and water vapor mixed with these gases. Examples include fuel gas.
炭化水素は特に限定されず、例えば、天然ガス、ナフサ、石炭ガス化ガス等が挙げられる。更に、メタン、エタン、プロパン、ブタン及びペンタン等の炭素数が１〜１０、好ましくは１〜７、より好ましくは１〜４の飽和炭化水素、並びにエチレン及びプロピレン等の不飽和炭化水素を主成分とするものが好ましく、飽和炭化水素を主成分とするものが更に好ましい。これらの燃料ガスは１種のみを用いてもよいし、２種以上を併用することもできる。また、５０体積％以下の窒素及びアルゴン等の不活性ガスを含有していてもよい。 The hydrocarbon is not particularly limited, and examples thereof include natural gas, naphtha, and coal gasification gas. Further, the main components are saturated hydrocarbons having 1 to 10, preferably 1 to 7, more preferably 1 to 4 carbon atoms such as methane, ethane, propane, butane and pentane, and unsaturated hydrocarbons such as ethylene and propylene. Those having a saturated hydrocarbon as a main component are more preferable. These fuel gas may use only 1 type and can also use 2 or more types together. Moreover, you may contain inert gas, such as nitrogen and argon of 50 volume% or less.
「酸化ガス」は、酸素と他の気体との混合ガス等が挙げられる。また、この混合ガスには８０体積％以下の窒素及びアルゴン等の不活性ガスが含有されていてもよい。これらの酸化ガスのうちでは安全であって、且つ安価であるため空気（約８０体積％の窒素が含まれている。）が好ましい。 Examples of the “oxidizing gas” include a mixed gas of oxygen and another gas. The mixed gas may contain 80% by volume or less of an inert gas such as nitrogen and argon. Of these oxidizing gases, air (containing about 80% by volume of nitrogen) is preferable because it is safe and inexpensive.
次に、図４、図５を参照し、本発明の特徴部分である固体電解質型燃料電池用電極の構成について説明する。
上述のように、アノードに用いる電極として、消失性固体材料を混合した電極ペーストを焼結して多数の気孔を形成した多孔質電極が一般に用いられているが、気孔の径や分布がばらついてガス拡散抵抗の低減を実現し難いという問題がある。
一方、図４に示すように、仮に消失性固体材料を用いずに、金属粒子２と、固体電解質体の第１セラミックス粒子４とからなる電極ペーストを焼結すると、焼結の初期では、２個の第１セラミックス粒子４が接しつつ、各セラミックス粒子４と、５個の金属粒子２との間に合計でＣ１〜Ｃ７の７個の接触点が形成され（図４（ａ））、これら接触点が３相界面を構成する。ところが、焼結が進むにつれ、２個の第１セラミックス粒子４が粒成長して結合し、１個の粗大粒となるため、金属粒子２との接触点の一部が失われる（接触点が４個（Ｃ１、Ｃ２、Ｃ４、Ｃ７）に減少する）（図４（ｂ））。このように、消失性固体材料を用いない場合、第１セラミックス粒子４の粒成長によって気孔の数、ひいては３相界面が減少してガス拡散抵抗の低減が図れない。
Next, the configuration of the solid oxide fuel cell electrode, which is a feature of the present invention, will be described with reference to FIGS.
As described above, a porous electrode in which a large number of pores are formed by sintering an electrode paste mixed with a disappearing solid material is generally used as an electrode for an anode, but the pore diameter and distribution vary. There is a problem that it is difficult to reduce the gas diffusion resistance.
On the other hand, as shown in FIG. 4, when an electrode paste composed of the metal particles 2 and the first ceramic particles 4 of the solid electrolyte body is sintered without using the vanishing solid material, at the initial stage of sintering, 2 A total of seven contact points C 1 to C 7 are formed between each ceramic particle 4 and the five metal particles 2 while the first ceramic particles 4 are in contact with each other (FIG. 4A). These contact points constitute a three-phase interface. However, as the sintering proceeds, the two first ceramic particles 4 grow and combine to form one coarse particle, so that a part of the contact point with the metal particle 2 is lost (the contact point is reduced). 4 (decrease to C 1 , C 2 , C 4 , C 7 ) (FIG. 4B). As described above, when the vanishing solid material is not used, the number of pores, and hence the three-phase interface is reduced by the grain growth of the first ceramic particles 4, and the gas diffusion resistance cannot be reduced.
そこで、図５に示すように、電極ペーストに第２セラミックス粒子６を添加して焼結すると、第１セラミックス粒子４に接した第２セラミックス粒子６が粒界に析出し、第１セラミックス粒子４の粒成長を抑制する。その結果、焼結が進んでも、各第１セラミックス粒子４と金属（又はその合金）粒子２との間の接触点（Ｃ１〜Ｃ７）が失われ難くなり、気孔（３相界面）が減少せずにガス拡散抵抗を低減することができる。又、消失性固体材料を用いずに気孔を形成するので、気孔の径や分布がばらつかず、ガス拡散抵抗を安定して低減することができる。
さらに、第１セラミックス粒子４と第２セラミックス粒子６とは焼結によって消失しないので、この点でも電極の気孔の径や分布のばらつきが少なくなる。又、第１セラミックス粒子４、第２セラミックス粒子６共に溶剤・バインダーとの濡れ性が良いため、分散性が向上し、結果、電極ペーストの塗布時のレべリング性（平坦性）が向上するので、電極厚みのばらつきも少なくなる。
なお、第１セラミックス粒子４は、安定化ジルコニア又は部分安定化ジルコニアからなる酸素イオン導電性のセラミックであるため、その粒成長を抑制することにより、気孔（３相界面）が減少せず、上記した効果を奏する。一方、第１セラミックス粒子４が完全ジルコニア（酸化ジルコニウムのみ）からなる場合、酸素イオン導電性を有しないため、気孔（３相界面）が形成されてもそもそも酸素イオンの取り込みができず、その粒成長を抑制してもガス拡散抵抗の低減には何ら寄与しない。従って、本発明では、第１セラミックス粒子４として安定化ジルコニア又は部分安定化ジルコニアを用いる。
Therefore, as shown in FIG. 5, when the second ceramic particles 6 are added to the electrode paste and sintered, the second ceramic particles 6 in contact with the first ceramic particles 4 are precipitated at the grain boundaries, and the first ceramic particles 4. Suppresses grain growth. As a result, even if the sintering proceeds, the contact points (C 1 to C 7 ) between the first ceramic particles 4 and the metal (or alloy) particles 2 are hardly lost, and pores (three-phase interface) are formed. The gas diffusion resistance can be reduced without decreasing. Further, since the pores are formed without using the disappearing solid material, the diameter and distribution of the pores do not vary, and the gas diffusion resistance can be stably reduced.
Furthermore, since the first ceramic particles 4 and the second ceramic particles 6 do not disappear by sintering, the pore size and distribution of the electrode are less varied in this respect as well. Further, since both the first ceramic particles 4 and the second ceramic particles 6 have good wettability with the solvent / binder, the dispersibility is improved, and as a result, the leveling property (flatness) at the time of applying the electrode paste is improved. Therefore, variations in electrode thickness are reduced.
The first ceramic particles 4 are oxygen ion conductive ceramics made of stabilized zirconia or partially stabilized zirconia. Therefore, by suppressing the grain growth, the pores (three-phase interface) are not reduced, Has the effect. On the other hand, when the first ceramic particle 4 is made of complete zirconia (only zirconium oxide), it does not have oxygen ion conductivity. Therefore, even if pores (three-phase interface) are formed, oxygen ions cannot be taken in the first place. Even if the growth is suppressed, it does not contribute to the reduction of the gas diffusion resistance. Therefore, in the present invention, stabilized zirconia or partially stabilized zirconia is used as the first ceramic particles 4.
固体電解質型燃料電池用電極に用いられる金属は、Ｎｉ、Ｃｏ、Ｒｕ、Ｆｅ、Ｃｕの群から選ばれる一種以上の金属またはその合金が挙げられる。
第１セラミックス粒子は、固体電解質体５と同一組成、つまり、ジルコニア（ＺｒＯ２）に安定化剤としてＹ２Ｏ３、ＣａＯ、Ｙｂ２Ｏ３、Ｓｃ２Ｏ３、Ｇｄ２Ｏ３、又はＮｄ２Ｏ３を添加してなる部分安定化ジルコニアとすることができる。又、ジルコニアへの上記した安定化剤の添加量を多くし、変態を完全に抑制した完全安定化ジルコニアとしてもよい。
第２セラミックス粒子は、Ａｌ２Ｏ３、ＭｇＯ、Ｌａ２Ｏ３、スピネル、ジルコン、ムライト及びコージェライトの群から選ばれる一種以上からなる。中でも、固体電解質体の主成分であるジルコニアとのイオン半径差や結晶構造差を考慮するとＡｌ２Ｏ３などのアルミナ系セラミックスがより好ましい。
Examples of the metal used for the solid oxide fuel cell electrode include one or more metals selected from the group consisting of Ni, Co, Ru, Fe, and Cu, or alloys thereof.
The first ceramic particles have the same composition as the solid electrolyte body 5, that is, Y 2 O 3 , CaO, Yb 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , or Nd as a stabilizer in zirconia (ZrO 2 ). Partially stabilized zirconia obtained by adding 2 O 3 can be obtained. Moreover, it is good also as fully stabilized zirconia which increased the addition amount of the above-mentioned stabilizer to zirconia, and completely suppressed transformation.
The second ceramic particles are made of one or more selected from the group consisting of Al 2 O 3 , MgO, La 2 O 3 , spinel, zircon, mullite, and cordierite. Among these, alumina ceramics such as Al 2 O 3 are more preferable in consideration of an ion radius difference and a crystal structure difference from zirconia which is a main component of the solid electrolyte body.
固体電解質型燃料電池用電極において、第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が０．１体積％以上５０体積％未満であることが好ましい。第２セラミックス粒子の含有割合が０．１体積％未満であると、電極を焼結する際に第１セラミックス粒子の粒成長を十分に抑制できず、気孔の数、ひいては３相界面が減少してガス拡散抵抗が増大する場合がある。一方、第２セラミックス粒子の含有割合が５０体積％を超えると、第１セラミックス粒子の焼結が抑制され過ぎ、第１セラミックス粒子間の結合が不足して電極の密着性が低下する場合がある。
より好ましくは、第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が３体積％以上４０体積％未満である。
In the electrode for a solid oxide fuel cell, it is preferable that the content ratio of the second ceramic particles is 0.1 volume% or more and less than 50 volume% with respect to the first ceramic particles. When the content ratio of the second ceramic particles is less than 0.1% by volume, the grain growth of the first ceramic particles cannot be sufficiently suppressed when the electrode is sintered, and the number of pores and thus the three-phase interface is reduced. Gas diffusion resistance may increase. On the other hand, when the content ratio of the second ceramic particles exceeds 50% by volume, the sintering of the first ceramic particles is excessively suppressed, and the bonding between the first ceramic particles is insufficient, and the electrode adhesion may be reduced. .
More preferably, the content ratio of the second ceramic particles is 3% by volume or more and less than 40% by volume with respect to the first ceramic particles.
なお、第１セラミックス粒子に対する第２セラミックス粒子の含有割合（体積％）は、燃料極の断面ＳＥＭにて、第１セラミックス粒子及び第２セラミックス粒子がそれぞれ占める断面積の割合で評価することができる。又、第２セラミックス粒子による第１セラミックス粒子の粒成長抑制効果は、第２セラミックス粒子と第１セラミックス粒子の相対的な体積割合によって影響されるため、上記した「体積％」を指標とすることが良い。一方、第１セラミックス粒子に対する第２セラミックス粒子の含有割合を質量％で表すと、第１セラミックス粒子と第２セラミックス粒子の密度が大きく異なる場合に、焼結抑制効果を反映しづらくなる。 The content ratio (volume%) of the second ceramic particles with respect to the first ceramic particles can be evaluated by the ratio of the cross-sectional areas occupied by the first ceramic particles and the second ceramic particles in the cross-sectional SEM of the fuel electrode. . Moreover, since the grain growth suppression effect of the first ceramic particles by the second ceramic particles is influenced by the relative volume ratio of the second ceramic particles and the first ceramic particles, the above-mentioned “volume%” is used as an index. Is good. On the other hand, when the content ratio of the second ceramic particles to the first ceramic particles is expressed by mass%, it is difficult to reflect the sintering suppression effect when the densities of the first ceramic particles and the second ceramic particles are greatly different.
本発明は上記実施形態に限定されず、固体電解質体に設けられるあらゆる固体電解質型燃料電池用電極及び固体電解質型燃料電池セルに適用可能である。 The present invention is not limited to the above-described embodiment, and can be applied to any solid electrolyte fuel cell electrode and solid electrolyte fuel cell provided in the solid electrolyte body.
次に、本発明の効果を確認するための試験に用いた実施例及び比較例について説明する。
まず、ＬａＯ、ＳｒＣＯ３、Ｃｏ３Ｏ４、Ｆｅ２Ｏ３、Ｓｍ２Ｏ３を所定量秤量した後に、ボールミルにてメタノールを溶媒として十分に湿式混合し、メタノールを蒸発させて混合粉を得た。
Next, examples and comparative examples used in tests for confirming the effects of the present invention will be described.
First, a predetermined amount of LaO, SrCO3, Co3O4, Fe2O3, and Sm2O3 was weighed, and then sufficiently wet-mixed using methanol as a solvent in a ball mill, and the methanol was evaporated to obtain a mixed powder.
次に、蓋のできるアルミナ製のるつぼに混合粉を入れて、昇温速度４℃／ｍｉｎにて、１２００℃で１時間仮焼した。得られた仮焼粉を解砕した後に、遊星ミルにて、平均粒径０．５μｍ、比表面積約５ｍ２／ｇの粉砕粉とし、これをバインダー溶液とよく混合して空気極ペーストを作成した。 Next, the mixed powder was put into an alumina crucible with a lid, and calcined at 1200 ° C. for 1 hour at a temperature rising rate of 4 ° C./min. After pulverizing the obtained calcined powder, it was made into a pulverized powder having an average particle size of 0.5 μm and a specific surface area of about 5 m 2 / g in a planetary mill, and this was mixed well with a binder solution to prepare an air electrode paste. .
また、定法により円盤状の固体電解質体（８ＹＳＺ）５を作成し、この固体電解質体５の表面に、反応防止層９を形成するために、サマリアドープセリアの薄膜を積層した。 In addition, a disk-shaped solid electrolyte body (8YSZ) 5 was prepared by a conventional method, and a thin film of samaria-doped ceria was laminated on the surface of the solid electrolyte body 5 in order to form the reaction preventing layer 9.
その後、この薄膜の上に、空気極ペーストをスクリーン印刷して塗布し、乾燥して溶媒を蒸発させた。次に、昇温速度５℃／ｍｉｎにて、１１００℃で１時間焼成し、この焼き付けにより、固体電解質体５の上に反応防止層９及び空気極７を形成した。尚、焼成後の固体電解質体５は、φ３０ｍｍ×厚み１ｍｍであり、空気極７はφ１３ｍｍである。 Thereafter, an air electrode paste was screen-printed and applied onto the thin film, and dried to evaporate the solvent. Next, baking was performed at 1100 ° C. for 1 hour at a heating rate of 5 ° C./min, and the reaction preventing layer 9 and the air electrode 7 were formed on the solid electrolyte body 5 by this baking. The solid electrolyte body 5 after firing has a diameter of 30 mm and a thickness of 1 mm, and the air electrode 7 has a diameter of 13 mm.
次に、燃料極の作成法を詳述する。
まず、遷移金属粒子、表１に示す組成の第１セラミックス粒子、表１に示す第２セラミックス粒子、バインダー（エチルセルロース）、及び溶剤（ブチルカルビトール）を混合して燃料極ペーストを調製した。表１に示した各粒子の焼結平均粒子径は、固体電解質型燃料電池用電極の断面ＳＥＭより求めた。より詳細には、断面をＳＥＭにより３５００倍程度で観察し、このＳＥＭ像から各粒子をスケッチし、各粒子の総面積を画像解析によって分析する。そして、この得られた各粒子の総面積を各粒子数で除した面積（各粒子１個あたりの面積（ＳＡ））の等価円の直径を平均粒子径（ＤＡ）と仮定する。数式を用いて表せば、以下の式（１）および（２）で表すことができる。
Next, a method for producing the fuel electrode will be described in detail.
First, transition metal particles, first ceramic particles having the composition shown in Table 1, second ceramic particles shown in Table 1, a binder (ethyl cellulose), and a solvent (butyl carbitol) were mixed to prepare a fuel electrode paste. The sintered average particle diameter of each particle shown in Table 1 was determined from the cross-sectional SEM of the electrode for the solid oxide fuel cell. More specifically, the cross section is observed by SEM at about 3500 times, each particle is sketched from this SEM image, and the total area of each particle is analyzed by image analysis. The diameter of the equivalent circle of the area obtained by dividing the total area of the obtained particles by the number of particles (area per one particle (SA)) is assumed to be the average particle diameter (DA). If expressed using mathematical formulas, they can be expressed by the following formulas (1) and (2).
各粒子１個あたりの面積（ＳＡ）＝各粒子の総面積／各粒子数…（１） Area per particle (SA) = total area of each particle / number of particles (1)
各粒子の平均粒子径（ＤＡ）＝２×√（ＳＧ／π）…（２） Average particle diameter (DA) of each particle = 2 × √ (SG / π) (2)
なお、表１にて、第１セラミックス粒子の配合量（ｗｔ％）は、遷移金属粒子に対する第１セラミックス粒子の含有割合を表す。又、第２セラミックス粒子の配合量（ｖｏｌ％）は、第１セラミックス粒子に対する第２セラミックス粒子の含有割合を示す。
そして、この燃料極ペーストを、固体電解質体５の裏面（空気極と反対の面）に塗布し、昇温速度５℃／ｍｉｎにて、１１００℃で１時間焼成することで、固体電解質体５の上に燃料極３を形成した。このようにして、比較例１及び実施例１〜２７の固体電解質型燃料電池セル１を製造した。
In Table 1, the blending amount (wt%) of the first ceramic particles represents the content ratio of the first ceramic particles with respect to the transition metal particles. Moreover, the compounding quantity (vol%) of 2nd ceramic particle shows the content rate of the 2nd ceramic particle with respect to 1st ceramic particle.
And this fuel electrode paste is apply | coated to the back surface (surface opposite to an air electrode) of the solid electrolyte body 5, and it baked at 1100 degreeC for 1 hour with the temperature increase rate of 5 degree-C / min, The solid electrolyte body 5 The fuel electrode 3 was formed on the top. Thus, the solid oxide fuel cell 1 of the comparative example 1 and Examples 1-27 was manufactured.
次に、電極の過電圧の評価として、製造した固体電解質型燃料電池セル１を大気中でセル温度をＳＯＦＣの運転温度である１０００℃に保って熱処理を行いながら、昇温直後と昇温後２００時間経過後に交流インピーダンス測定し、コールコールプロット（Ｃｏｌｅ−Ｃｏｌｅ
Ｐｌｏｔ)を得た。
比較例１の電極抵抗の変化率を基準とし、得られたコールコールプロットから算出した電極抵抗の変化率が比較例１より減少した割合が１０％未満（比較例１より増加した場合を含む）の場合を評価△とし、比較例１より１０％以上２０％未満減少した場合を評価○とし、比較例１より２０％以上減少した場合を評価◎とした。
また、電極の密着性の評価として、固体電解質型燃料電池セル１の通常制御状態にて、室温と８００℃との間でガスセンサ１のオンオフを３００００サイクル行った。試験後の電極間電圧を測定した。、比較例１の電極間電圧の変化率を基準とし、得られた電極間電圧の変化率が比較例１より５％以上高い場合を評価△とし、電極間電圧の変化率が比較例１より５％未満である場合を評価○とした。
実施例１と同様の評価を実施例２〜実施例２７に対しても行った。
得られた結果を表１に示す。
Next, as an evaluation of the overvoltage of the electrode, the manufactured solid oxide fuel cell 1 was subjected to heat treatment in the atmosphere while maintaining the cell temperature at 1000 ° C. which is the operating temperature of SOFC, and immediately after the temperature increase and after the temperature increase 200 AC impedance is measured after a lapse of time, and the Cole-Cole plot (Cole-Cole
Plot).
Based on the change rate of the electrode resistance of Comparative Example 1, the ratio of the change rate of the electrode resistance calculated from the obtained Cole-Cole plot is less than 10% (including the case where the change rate is higher than that of Comparative Example 1). The case of [Delta] was evaluated as [Delta], the case where it was reduced by 10% or more and less than 20% from Comparative Example 1 was evaluated as "Good", and the case where it was reduced from Comparative Example 1 by 20% or more was evaluated as "Good".
As an evaluation of electrode adhesion, the gas sensor 1 was turned on and off at 30,000 cycles between room temperature and 800 ° C. in the normal control state of the solid oxide fuel cell 1. The voltage between the electrodes after the test was measured. Based on the change rate of the interelectrode voltage of Comparative Example 1, the case where the obtained change rate of the interelectrode voltage was 5% or more higher than that of Comparative Example 1 was evaluated as Δ, and the change rate of the interelectrode voltage was higher than that of Comparative Example 1. The case where it was less than 5% was evaluated as ○.
The same evaluation as in Example 1 was performed for Examples 2 to 27.
The obtained results are shown in Table 1.
表１から明らかなように、遷移金属粒子と、第１セラミックス粒子と、第２セラミックス粒子と、を焼結してなる電極を燃料極に用いた実施例７〜２７の場合、過電圧の低減効果が大きく、換言すると、過電圧特性に優れると共に、電極の密着性も良好であった。
一方、第２セラミックス粒子を用いずに電極を形成した比較例１の場合、過電圧の低減効果が小さく、換言すると、過電圧特性に劣った。
また、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が０．０８体積％である実施例３の場合も、過電圧特性に劣った。
一方、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が０．１体積％である実施例１４、及び、第２セラミックス粒子の含有割合が５０体積％である実施例７の場合は、過電圧特性に優れると共に、電極の密着性も良好であった。
そして、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が５３体積％である実施例４の場合、過電圧特性に優れるものの、電極の密着性に劣った。これは、第１セラミックス粒子の焼結が抑制され過ぎ、第１セラミックス粒子間の結合が不足したためと考えられる。
これらの結果より、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が０．１体積％以上５０体積％未満であることが好ましいことがわかる。
As apparent from Table 1, in the case of Examples 7 to 27 in which an electrode formed by sintering transition metal particles, first ceramic particles, and second ceramic particles was used as a fuel electrode, the effect of reducing overvoltage In other words, in addition to excellent overvoltage characteristics, the electrode adhesion was also good.
On the other hand, in the case of Comparative Example 1 in which the electrodes were formed without using the second ceramic particles, the overvoltage reduction effect was small, in other words, the overvoltage characteristics were inferior.
Further, in the case of Example 3 in which the content ratio of the second ceramic particles was 0.08% by volume with respect to the first ceramic particles in the electrode, the overvoltage characteristics were inferior.
On the other hand, with respect to the first ceramic particles in the electrode, Example 14 in which the content ratio of the second ceramic particles is 0.1% by volume and Example 7 in which the content ratio of the second ceramic particles is 50% by volume. In this case, the overvoltage characteristics were excellent, and the electrode adhesion was also good.
In Example 4 in which the content ratio of the second ceramic particles was 53% by volume with respect to the first ceramic particles in the electrode, the overvoltage characteristics were excellent, but the electrode adhesion was poor. This is considered to be because the sintering of the first ceramic particles was excessively suppressed and the bonding between the first ceramic particles was insufficient.
From these results, it can be seen that the content ratio of the second ceramic particles is preferably 0.1% by volume or more and less than 50% by volume with respect to the first ceramic particles in the electrode.
また、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が１体積％である実施例１６に対し、第２セラミックス粒子の含有割合が３体積％である実施例１５は、過電圧特性により優れる。
そして、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が５０体積％である実施例７に対し、第２セラミックス粒子の含有割合が４０体積％である実施例８は、過電圧特性により優れる。
この結果より、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が３体積％以上４０体積％未満であることがより好ましいことがわかる。
Further, in contrast to Example 16 in which the content ratio of the second ceramic particles is 1% by volume with respect to the first ceramic particles in the electrode, Example 15 in which the content ratio of the second ceramic particles is 3% by volume is an overvoltage. Excellent characteristics.
And with respect to the 1st ceramic particle in an electrode, Example 8 whose content rate of a 2nd ceramic particle is 40 volume% with respect to Example 7 whose content rate of a 2nd ceramic particle is 50 volume% is overvoltage. Excellent characteristics.
From this result, it is understood that the content ratio of the second ceramic particles is more preferably 3% by volume or more and less than 40% by volume with respect to the first ceramic particles in the electrode.
また、焼結平均粒子径が０．８μｍの第１セラミックス粒子に対し、第２セラミックス粒子の焼結平均粒子径が０．０７μｍである実施例１の場合、過電圧特性に劣った。これに対し、焼結平均粒子径が０．８μｍの第１セラミックス粒子に対し、第２セラミックス粒子の焼結平均粒子径が０．０８μｍである実施例１２の場合、過電圧特性に優れた。
そして、焼結平均粒子径が０．８μｍの第１セラミックス粒子に対し、第２セラミックス粒子の焼結平均粒子径が０．８５μｍである実施例２の場合、過電圧特性に優れるものの、電極の密着性に劣った。これは、第１セラミックス粒子の焼結が抑制され過ぎ、第１セラミックス粒子間の結合が不足したためと考えられる。一方、焼結平均粒子径が０．８μｍの第１セラミックス粒子に対し、第２セラミックス粒子の焼結平均粒子径が０．８μｍである実施例１３の場合、過電圧特性に優れると共に、電極の密着性も良好であった。
この結果より、第２セラミックス粒子の焼結平均粒子径は、前記第１セラミックス粒子の０．１倍以上１倍以下であることが好ましいことがわかる。
Further, in the case of Example 1 in which the sintered average particle diameter of the second ceramic particles was 0.07 μm with respect to the first ceramic particles having a sintered average particle diameter of 0.8 μm, the overvoltage characteristics were inferior. On the other hand, in the case of Example 12 in which the sintered average particle size of the second ceramic particles was 0.08 μm with respect to the first ceramic particles having a sintered average particle size of 0.8 μm, the overvoltage characteristics were excellent.
In the case of Example 2 in which the sintered average particle size of the second ceramic particles is 0.85 μm with respect to the first ceramic particles having a sintered average particle size of 0.8 μm, the overvoltage characteristics are excellent, but the adhesion of the electrodes Inferior. This is considered to be because the sintering of the first ceramic particles was excessively suppressed and the bonding between the first ceramic particles was insufficient. On the other hand, in the case of Example 13 in which the sintered average particle diameter of the second ceramic particles is 0.8 μm with respect to the first ceramic particles having a sintered average particle diameter of 0.8 μm, the overvoltage characteristics are excellent, and the adhesion of the electrode The property was also good.
From this result, it is found that the sintered average particle diameter of the second ceramic particles is preferably 0.1 to 1 times that of the first ceramic particles.
また、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が１０体積％であり、電極厚みが０．５μｍの実施例５に対し、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が１０体積％であり、電極厚みが１μｍである実施例１１の場合、過電圧特性がより向上した。
また、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が１０体積％であり、電極厚みが２５μｍの実施例６に対し、電極中の第１セラミックス粒子に対し、第２セラミックス粒子の含有割合が１０体積％であり、電極厚みが２０μｍである実施例１０の場合、過電圧特性がより向上した。
この結果より、電極の厚みが１〜２０μｍ以上であることが好ましいことがわかる。
Further, the content ratio of the second ceramic particles to the first ceramic particles in the electrode is 10% by volume and the thickness of the electrode is 0.5 μm. In the case of Example 11 in which the content ratio of 2 ceramic particles was 10% by volume and the electrode thickness was 1 μm, the overvoltage characteristics were further improved.
Moreover, the content rate of the 2nd ceramic particle is 10 volume% with respect to the 1st ceramic particle in an electrode, and 2nd ceramic with respect to the 1st ceramic particle in an electrode with respect to Example 6 whose electrode thickness is 25 micrometers. In Example 10 in which the content ratio of the particles was 10% by volume and the electrode thickness was 20 μm, the overvoltage characteristics were further improved.
From this result, it is understood that the thickness of the electrode is preferably 1 to 20 μm or more.
また、第１セラミックス粒子の種類がＳＤＣである実施例１７やＧＤＣである実施例１８においても、実施例９と同様、過電圧特性に優れると共に、電極の密着性も良好であった。
また、第２セラミックス粒子の種類がＭｇＯである実施例１９、Ｌａ２Ｏ３である実施例２０、スピネルである実施例２１、ジルコンである実施例２２、ムライトである実施例２３、コージェライトである実施例２４、アルミナとＭｇＯの混合物である実施例２５においても、実施例９と同様、過電圧特性に優れると共に、電極の密着性も良好であった。
また、遷移金属の種類がＣｏである実施例２６やＲｕである実施例２７においても、実施例９と同様、過電圧特性に優れると共に、電極の密着性も良好であった。
Further, in Example 17 where the type of the first ceramic particles is SDC and Example 18 which is GDC, as in Example 9, the overvoltage characteristics were excellent and the electrode adhesion was also good.
In addition, Example 19 in which the kind of the second ceramic particles is MgO, Example 20 in which La2O3 is used, Example 21 in which spinel is used, Example 22 in which zircon is used, Example 23 in which mullite is used, Example in which cordierite is used In Example 25, which is a mixture of 24 and alumina and MgO, as in Example 9, the overvoltage characteristics were excellent and the adhesion of the electrodes was also good.
Further, in Example 26 in which the type of transition metal is Co and Example 27 in which Ru is Ru, as in Example 9, the overvoltage characteristics were excellent and the electrode adhesion was also good.
図６、図７に、それぞれ実施例１５、比較例１の燃料極３の断面Ｃの走査電子顕微鏡（ＳＥＭ）像を示す。なお、図６、図７は二次電子像（組成像）であり、断面Ｃにおける灰色部分が第１セラミックス粒子を表し、白い部分が遷移金属粒子（Ｎｉ）を表す。又、断面Ｃより上の部分は固体電解質体を表す。
灰色部分の粒の大きさは、実施例１５の方が比較例１より小さく、第１セラミックス粒子の粒成長が抑制されていることがわかる。
6 and 7 show scanning electron microscope (SEM) images of the cross section C of the fuel electrode 3 of Example 15 and Comparative Example 1, respectively. 6 and 7 are secondary electron images (composition images), in which the gray portion in the cross section C represents the first ceramic particles, and the white portion represents the transition metal particles (Ni). The portion above the cross section C represents a solid electrolyte body.
The size of the gray portion grains is smaller in Example 15 than in Comparative Example 1, indicating that grain growth of the first ceramic particles is suppressed.
１ 固体電解質型燃料電池スタック
２ 遷移金属又はその合金の粒子
４ 第１セラミックス粒子
６ 第２セラミックス粒子
DESCRIPTION OF SYMBOLS 1 Solid oxide fuel cell stack 2 Transition metal or its alloy particle 4 1st ceramic particle 6 2nd ceramic particle
Claims (6)
Ｎｉ、Ｃｏ、Ｒｕ、Ｆｅ、Ｃｕの群から選ばれる１種以上の金属又はその合金の粒子と、安定化ジルコニア、部分安定化ジルコニア、セリアの中から選ばれる第１セラミックス粒子と、Ａｌ２Ｏ３、ＭｇＯ、Ｌａ２Ｏ３、スピネル、ジルコン、ムライト及びコージェライトの群から選ばれる１種以上の第２セラミックス粒子と、からなり、
前記第２セラミックス粒子は、前記第１セラミックス粒子よりも含有量が少なく、
前記第１セラミックス粒子に対し、前記第２セラミックス粒子の含有割合が０．１体積％以上５０体積％未満であり、
前記第２セラミックス粒子の焼結平均粒子径は、前記第１セラミックス粒子の０．１倍以上１倍以下であり、
前記第１セラミックス粒子同士の間に前記第２セラミックス粒子が配置されている
ことを特徴とする固体電解質型燃料電池用電極。 An electrode for a solid oxide fuel cell provided on the surface of a solid electrolyte body mainly composed of zirconia,
Particles of one or more metals selected from the group consisting of Ni, Co, Ru, Fe and Cu, or alloys thereof; first ceramic particles selected from stabilized zirconia, partially stabilized zirconia and ceria; and Al 2 O 3 , MgO, La 2 O 3 , spinel, zircon, mullite, and one or more second ceramic particles selected from the group of cordierite,
The second ceramic particles have a lower content than the first ceramic particles,
The content ratio of the second ceramic particles with respect to the first ceramic particles is 0.1 volume% or more and less than 50 volume%,
The sintered average particle diameter of the second ceramic particles is 0.1 to 1 times that of the first ceramic particles,
The electrode for a solid oxide fuel cell, wherein the second ceramic particles are disposed between the first ceramic particles.
前記一対の電極のうち、いずれか一方の電極として、請求項１〜３のいずれかに記載の固体電解質型燃料電池用電極を用いる固体電解質型燃料電池セル。 A solid electrolyte fuel cell comprising at least a solid electrolyte body and a pair of electrodes provided on the solid electrolyte body,
A solid oxide fuel cell using the electrode for a solid oxide fuel cell according to any one of claims 1 to 3 as one of the pair of electrodes.
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