JP2003022821A - Scandia stabilized zirconia electrolyte - Google Patents
Scandia stabilized zirconia electrolyteInfo
- Publication number
- JP2003022821A JP2003022821A JP2001208336A JP2001208336A JP2003022821A JP 2003022821 A JP2003022821 A JP 2003022821A JP 2001208336 A JP2001208336 A JP 2001208336A JP 2001208336 A JP2001208336 A JP 2001208336A JP 2003022821 A JP2003022821 A JP 2003022821A
- Authority
- JP
- Japan
- Prior art keywords
- scandia
- stabilized zirconia
- mass
- oxide
- conductivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910002076 stabilized zirconia Inorganic materials 0.000 title claims abstract description 59
- 239000003792 electrolyte Substances 0.000 title claims abstract description 38
- 241000968352 Scandia <hydrozoan> Species 0.000 title claims abstract description 36
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000004449 solid propellant Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 43
- -1 oxygen ion Chemical class 0.000 abstract description 18
- 230000008859 change Effects 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 12
- 230000014759 maintenance of location Effects 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 74
- 239000000843 powder Substances 0.000 description 51
- 239000011230 binding agent Substances 0.000 description 23
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- 238000000034 method Methods 0.000 description 18
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 17
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
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- 239000007784 solid electrolyte Substances 0.000 description 10
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- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
(57)【要約】
【課題】 スカンジア安定化ジルコニア電解質の高温長
時間使用時における酸素イオン導電率の経時変化を少な
くし、安定して高い導電性を持続すると共に、優れた高
温強度と強度持続性を有する燃料電池用のスカンジア安
定化ジルコニア電解質を提供すること。
【解決手段】 スカンジア安定化ジルコニアにおいて、
４Ａ族、５Ａ族、７Ａ族および４Ｂ族元素よりなる群か
ら選択される少なくとも１種の酸化物を、スカンジア安
定化ジルコニアに対し０．０１〜５質量％含有する固体
酸化物型燃料電池用スカンジア安定化ジルコニア電解質
を開示する。(57) [Summary] [PROBLEMS] To reduce the change with time of oxygen ion conductivity over time when a scandia-stabilized zirconia electrolyte is used at a high temperature for a long time, maintain high conductivity stably, and have excellent high-temperature strength and strength retention. Disclosed is a scandia-stabilized zirconia electrolyte for a fuel cell having a susceptibility. SOLUTION: In scandia stabilized zirconia,
Scandia for solid oxide fuel cells containing at least one oxide selected from the group consisting of Group 4A, 5A, 7A and 4B elements based on scandia stabilized zirconia in an amount of 0.01 to 5% by mass. A stabilized zirconia electrolyte is disclosed.
Description
【０００１】[0001]
【発明の属する技術分野】本発明はスカンジア安定化ジ
ルコニア電解質に関し、特に安定して優れた酸素イオン
導電性を示すと共に、ハンドリングに十分な機械的強度
を有し、燃料電池用の固体電解質膜用として優れた性能
を有するスカンジア安定化ジルコニア電解質に関するも
のである。TECHNICAL FIELD The present invention relates to a scandia-stabilized zirconia electrolyte, and particularly to a solid electrolyte membrane for a fuel cell, which exhibits stable and excellent oxygen ion conductivity and has sufficient mechanical strength for handling. The present invention relates to a scandia-stabilized zirconia electrolyte having excellent performance as.
【０００２】[0002]
【従来の技術】固体酸化物型燃料電池の電解質として、
立方晶のジルコニア系セラミックスや正方晶のジルコニ
ア系セラミックスが広く検討されており、該セラミック
スの結晶構造を安定化するための安定化剤としては、イ
ットリアが一般的に使用されている。As an electrolyte for a solid oxide fuel cell,
Cubic zirconia ceramics and tetragonal zirconia ceramics have been widely studied, and yttria is generally used as a stabilizer for stabilizing the crystal structure of the ceramics.
【０００３】しかしジルコニア系セラミックスの酸素イ
オン導電性は、添加する金属イオンの半径や固溶量によ
って異なり、イットリアを固溶させたジルコニアよりも
スカンジアを固溶させたジルコニアの方が高い導電性を
持つ可能性が示されている。また、固体酸化物型燃料電
池発電システムを実用化していくには、他の発電システ
ム等に比肩し得る経済性と優れた発電性能に加えて、少
なくとも４０，０００時間以上といった長時間の高温耐
久性が要求される。However, the oxygen ion conductivity of zirconia-based ceramics differs depending on the radius and the amount of solid solution of metal ions to be added, and the conductivity of zirconia containing scandia as a solid solution is higher than that of zirconia containing yttria as a solid solution. Possibility to have. In addition, in order to put the solid oxide fuel cell power generation system into practical use, in addition to the economical efficiency and excellent power generation performance comparable to other power generation systems, etc., high temperature durability of at least 40,000 hours or more Sex is required.
【０００４】そこで、燃料電池の固体電解質膜としてイ
ットリア安定化ジルコニア（ＹＳＺ）よりも低コストで
優れた発電性能を実現すべく、種々研究が進められてお
り、イットリア安定化ジルコニアよりも高い酸素イオン
導電性を有するスカンジア安定化ジルコニアセラミック
スが注目されている。Therefore, various studies have been carried out in order to realize a power generation performance superior to yttria-stabilized zirconia (YSZ) as a solid electrolyte membrane of a fuel cell, and oxygen ions higher than yttria-stabilized zirconia. Scandia-stabilized zirconia ceramics, which has electrical conductivity, has attracted attention.
【０００５】例えば、スカンジア安定化ジルコニア（Ｓ
ｃＳＺ）にアルミナを添加した三元系金属酸化物からな
るセラミックス製の酸素イオン導電体が知られている。
そしてこのセラミックスは、副ドーパントとして特定比
率のアルミナを添加し結晶構造を安定化したもので、室
温と高温の作動温度の間で構造変態を起こすことがな
く、イットリア安定化ジルコニアよりも高いイオン導電
性を有しており、燃料電池用の固体電解質としても実用
可能な酸素イオン導電体になり得ると考えられる。For example, scandia-stabilized zirconia (S
A ceramic oxygen ion conductor made of a ternary metal oxide obtained by adding alumina to cSZ) is known.
This ceramic has a crystal structure stabilized by adding alumina in a specific ratio as a sub-dopant, does not undergo structural transformation between room temperature and high operating temperature, and has a higher ionic conductivity than yttria-stabilized zirconia. It is considered that the oxygen ion conductor has the properties and can be practically used as a solid electrolyte for fuel cells.
【０００６】また、スカンジア安定化ジルコニア（Ｓｃ
ＳＺ）に、原子価が２価または３価で安定な副ドーパン
トであるＭ2Ｏ3（Ｍは金属元素を示す）を添加した三元
系金属酸化物からなる酸素イオン導電体も知られてい
る。Further, scandia-stabilized zirconia (Sc
An oxygen ion conductor composed of a ternary metal oxide obtained by adding M 2 O 3 (M represents a metal element), which is a stable sub-dopant having divalent or trivalent valence, to SZ) is also known. There is.
【０００７】この副ドーパントは、上記金属ＭがＩｎ，
Ｇａ，Ｔｉ，Ｖ，Ｃｒ，Ｆｅ，Ｃｏ，Ｍｇ，Ｃａ，Ｚ
ｎ，Ｓｒ，Ｂａの中から選ばれる１種であり、これらが
添加されることによって、Ｓｃの特性を保持しつつ、な
おかつ結晶構造は立方晶で安定化されて高温での結晶変
態が現れず、高イオン導電性で且つ熱サイクルを受けた
ときの強度持続性にも優れたものとなる。This sub-dopant is composed of the metal M of In,
Ga, Ti, V, Cr, Fe, Co, Mg, Ca, Z
It is one kind selected from n, Sr, and Ba, and by adding these, while maintaining the characteristics of Sc, the crystal structure is stabilized by cubic crystal and the crystal transformation does not appear at high temperature. It also has high ionic conductivity and excellent strength durability when subjected to a heat cycle.
【０００８】しかし何れにも、発電特性を長期的に持続
させる上で重要な要件の１つである酸素イオン導電性の
経時変化については記載されていない。However, none of them describes the change over time in oxygen ion conductivity, which is one of the important requirements for maintaining the power generation characteristics for a long period of time.
【０００９】一方、“Ｓｏｌｉｄ Ｓｔａｔｅ Ｉｏｎ
ｉｃｓ”の７２巻、２７１−２７５頁（１９９４年）、
７９巻、１３７−１４２頁（１９９５年）、１３２巻、
２３５−２３９頁（２０００年）には、スカンジア量を
２．９〜１２モル％の範囲で変化させたスカンジア安定
化ジルコニア（２．９〜１２ＳｃＳＺ）、２０質量％の
アルミナを添加した８〜１１モル％スカンジア安定化ジ
ルコニア（８〜１１ＳｃＳＺ２０Ａ）について、導電性
の経時変化が検討されている。その中で、結晶構造が菱
面体である１１〜１２ＳｃＳＺや１１ＳｃＳＺ２０Ａ
は、１０００℃で４０００〜６０００時間の長時間曝露
でも殆ど経時変化が見られない。On the other hand, "Solid State Ion
ics ”, 72, 271-275 (1994),
79, 137-142 (1995), 132,
Pp. 235-239 (2000), scandia-stabilized zirconia (2.9-12ScSZ) in which the amount of scandia was changed in the range of 2.9-12 mol%, and 8-11 in which 20 mass% of alumina was added. With respect to mol% scandia-stabilized zirconia (8 to 11 ScSZ20A), changes in conductivity over time have been investigated. Among them, 11-12ScSZ and 11ScSZ20A having a rhombohedral crystal structure.
Shows almost no change with time even after long-term exposure at 1000 ° C. for 4000 to 6000 hours.
【００１０】しかし立方晶構造である８ＳｃＳＺは、１
０００℃で１３００時間の曝露で導電率が０．３２Ｓ／
ｃｍから０．１４Ｓ／ｃｍに低下することが報告されて
いる。また、正方晶構造である２．９ＳｃＳＺは１００
０℃で１０００時間の曝露で導電率が０．０９Ｓ／ｃｍ
から０．０６３Ｓ／ｃｍに低下することが報告されてい
る。即ちこれらは、１０００〜１３００時間の曝露で導
電率が３０〜６０％大きく低下していることになる。However, the cubic structure 8ScSZ is 1
Conductivity of 0.32 S / after exposure for 1300 hours at 000 ° C
It has been reported to decrease from cm to 0.14 S / cm. In addition, the tetragonal structure of 2.9ScSZ is 100.
Conductivity of 0.09 S / cm after exposure at 0 ° C for 1000 hours
To 0.063 S / cm have been reported. That is, the electrical conductivity of these is greatly reduced by 30 to 60% after exposure for 1000 to 1300 hours.
【００１１】上記の様にアルミナは、分散強化剤として
優れた特性を有しているが、反面アルミナは反応性が高
いため、ジルコニア電解質シートの表層部にアルミナが
存在すると、高温に長時間曝されたときに、電極成分中
に含まれる遷移金属や希土類元素との間で固相反応を起
こし、新たにアルミナ系の複合酸化物を生成することが
ある。例えばアノードにＮｉ成分が存在する場合は、Ｎ
ｉＡｌ2Ｏ4（スピネル結晶系）が生成し易くなる。ま
た、カソードにＭｎ成分が存在する場合は、ＭｎＡｌＯ
3（ペロブスカイト結晶系）が生成し易くなる。これら
がジルコニア電解質シートの表層部に存在すると、異物
となってジルコニアとの熱膨張差によりジルコニア電解
質シートの割れの起点となり、強度劣化の原因となる。
この様なことから、アルミナは電解質用ジルコニアの分
散強化剤として好ましいものとはいい難い。As described above, alumina has excellent properties as a dispersion strengthening agent, but on the other hand, since alumina has high reactivity, when alumina is present in the surface layer of the zirconia electrolyte sheet, it is exposed to high temperatures for a long time. When this occurs, a solid-phase reaction may occur with the transition metal or rare earth element contained in the electrode component, and a new alumina-based composite oxide may be generated. For example, when Ni component is present in the anode, N
iAl 2 O 4 (spinel crystal system) is easily generated. When the cathode contains Mn component, MnAlO
3 (perovskite crystal system) is easily generated. When these are present in the surface layer of the zirconia electrolyte sheet, they become foreign matter and become a starting point of cracking of the zirconia electrolyte sheet due to a difference in thermal expansion with zirconia, which causes strength deterioration.
From the above, it is difficult to say that alumina is preferable as a dispersion strengthening agent for zirconia for electrolyte.
【００１２】また燃料電池発電システムに用いる固体電
解質としては、高い酸素イオン導電性と共に、長時間、
たとえば４０，０００時間といったレベルまでその高い
酸素イオン導電性を安定に維持することが重要であり、
イオン導電率の低下率を小さく抑え、高レベルの電気特
性を長時間持続せしめ得る様な改質が望まれる。Further, as a solid electrolyte used in a fuel cell power generation system, high oxygen ion conductivity,
It is important to keep its high oxygen ion conductivity stable up to the level of 40,000 hours,
A modification that suppresses the reduction rate of ionic conductivity to a small extent and can maintain a high level of electrical characteristics for a long time is desired.
【００１３】即ち、燃料電池システムに用いられるスカ
ンジア安定化ジルコニア中に配合する酸化物について
は、その種類などを含めて更に検討の余地があり、ま
た、得られる燃料電池用スカンジア安定化ジルコニアの
結晶構造や強度、更には、これを用いた燃料電池用スカ
ンジア安定化ジルコニア電解質の導電性の経時変化など
についても、同様に検討の余地が残されている。That is, there is room for further study on the oxide compounded in the scandia-stabilized zirconia used in the fuel cell system, including the type of the oxide, and the obtained crystal of scandia-stabilized zirconia for a fuel cell. The structure and strength, as well as the temporal change in the conductivity of the scandia-stabilized zirconia electrolyte for fuel cells using the same, leave room for study.
【００１４】[0014]
【発明が解決しようとする課題】本発明は上記の様な事
情に着目してなされたもので、その目的は、スカンジア
安定化ジルコニア電解質の高温長時間使用時における酸
素イオン導電率の経時変化を少なくし、安定して高い導
電性を持続し、特に２０００時間までの初期導電率の劣
化程度を低減すると共に、優れた高温強度と強度持続性
を有するスカンジア安定化ジルコニア電解質を提供する
ことにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its purpose is to examine the change with time of the oxygen ion conductivity of a scandia-stabilized zirconia electrolyte at high temperature for a long time. It is to provide a scandia-stabilized zirconia electrolyte that has a high level of high temperature strength and strength durability while reducing the amount of deterioration, the stability of the initial conductivity up to 2000 hours in particular, and maintaining high conductivity stably. .
【００１５】また、新エネルギー・産業技術総合開発機
構（ＮＥＤＯ）における平成１３年度からの「固体酸化
物形燃料電池の研究開発」の開発目標として、熱自立モ
ジュールの目標性能が、初期特性評価と同じ条件で３０
００時間の発電を行なったときの電圧低下率が「０．２
５％／１０００時間」以下（平成１２年度「高温形燃料
電池発電技術」研究開発成果報告会講演要旨集（ＮＥＤ
Ｏ、燃料・貯蔵技術開発室、平成１３年２月２７日）と
計画されていることからも、固体電解質として酸素イオ
ン導電率の経時劣化が電圧低下率に大きく影響しない様
なスカンジア安定化ジルコニア電解質を提供することに
ある。As a development target of "Research and development of solid oxide fuel cell" from the 2001 fiscal year in the New Energy and Industrial Technology Development Organization (NEDO), the target performance of the thermal self-supporting module is the initial characteristic evaluation and 30 under the same conditions
The voltage drop rate when power is generated for 00 hours is "0.2
5% / 1000 hours or less (Abstracts of the lectures on the research and development results report of "High-temperature fuel cell power generation technology"
O, Fuel and Storage Technology Development Office, February 27, 2001), the scandia-stabilized zirconia is a solid electrolyte in which deterioration over time of oxygen ion conductivity does not significantly affect the voltage drop rate. It is to provide an electrolyte.
【００１６】[0016]
【課題を解決するための手段】本発明者らは上記の様な
課題の下で、スカンジア安定化ジルコニアに配合する酸
化物の種類と、得られる配合物である燃料電池用のスカ
ンジア安定化ジルコニア電解質の結晶構造と導電性の経
時変化に主眼を置いて検討を進めた結果、これら両特性
を満たす燃料電池用スカンジア電解質を得ることに成功
した。Under the above-mentioned problems, the present inventors have investigated the kind of oxide to be added to scandia-stabilized zirconia and the resulting compound, scandia-stabilized zirconia for fuel cells. As a result of further studies focusing on changes in the crystal structure and conductivity of the electrolyte over time, we succeeded in obtaining a scandia electrolyte for fuel cells that satisfies both of these characteristics.
【００１７】即ち、上記課題を解決することのできた本
発明に係る燃料電池用のスカンジア安定化ジルコニア電
解質とは、スカンジアで安定化されると共に、４Ａ族、
５Ａ族、７Ａ族および４Ｂ族元素の酸化物よりなる群か
ら選択される少なくとも１種を、スカンジア安定化ジル
コニアに対して０．０１〜５質量％含有するところに要
旨を有している。That is, the scandia-stabilized zirconia electrolyte for a fuel cell according to the present invention, which has been able to solve the above-mentioned problems, includes scandia-stabilized zirconia electrolyte, Group 4A,
The gist is that at least one selected from the group consisting of oxides of 5A group, 7A group, and 4B group elements is contained in an amount of 0.01 to 5 mass% with respect to scandia-stabilized zirconia.
【００１８】更に具体的には、上記燃料電池用のスカン
ジア安定化ジルコニアは、３〜１５モル％のスカンジア
で安定化されると共に、原子価が４価もしくは５価であ
る元素の酸化物であるＴｉＯ2、Ｎｂ2Ｏ5、Ｔａ2Ｏ5お
よびＭｎＯ2よりなる群から選択される少なくとも１種
を、スカンジア安定化ジルコニアに対し０．０１〜５質
量％含有するものが好ましい。More specifically, the scandia-stabilized zirconia for fuel cells is an oxide of an element which is stabilized with 3 to 15 mol% of scandia and has a valence of 4 or 5. It is preferable that at least one selected from the group consisting of TiO 2 , Nb 2 O 5 , Ta 2 O 5 and MnO 2 is contained in an amount of 0.01 to 5% by mass based on scandia-stabilized zirconia.
【００１９】また本発明の上記電解質においては、酸化
ケイ素、および／またはＮａ，Ｋ，Ｒｂ，Ｃｓの如きア
ルカリ金属の酸化物の含有量を極力少なく抑えることが
望ましく、好ましくは何れも０．１質量％以下、より好
ましくは０．０５質量％以下に抑えることが望ましい。In the above-mentioned electrolyte of the present invention, it is desirable that the content of silicon oxide and / or the oxide of an alkali metal such as Na, K, Rb, Cs be suppressed to a minimum, and preferably 0.1%. It is desirable to control the content to be not more than mass%, more preferably not more than 0.05 mass%.
【００２０】[0020]
【発明の実施の形態】前述した様な課題の下で本発明者
らは、スカンジアで安定化されたジルコニア電解質を対
象とし、該電解質の導電率の経時変化を少なくしてより
耐久性に優れた電解質を得るべく、様々の角度から研究
を進めてきた。DETAILED DESCRIPTION OF THE INVENTION Under the above-mentioned problems, the inventors of the present invention are directed to scandia-stabilized zirconia electrolytes and reduce the change with time of the conductivity of the electrolytes to obtain more excellent durability. We have been conducting research from various angles in order to obtain a good electrolyte.
【００２１】その結果、導電率の経時変化は結晶構造の
変化とグレイン粒子径の安定性に大きく影響され、スカ
ンジア安定化ジルコニアにある特定の酸化物を特定量含
有させれば、初期導電性を若干低下させるだけで、その
後の導電性の経時変化を小さく抑え得ることを見出し、
上記本発明に想到したものである。As a result, the change in conductivity with time is greatly influenced by the change in crystal structure and the stability of grain particle size, and if a specific amount of a specific oxide in scandia-stabilized zirconia is contained, the initial conductivity is improved. It was found that the conductivity change with time can be suppressed to a small level by only slightly lowering it.
The present invention has been conceived.
【００２２】また上記特定の酸化物は、スカンジア安定
化ジルコニアセラミックスに対し分散強化剤としても作
用し、結果として優れた高温強度と強度持続性を与える
ことも見出した。It has also been found that the above-mentioned specific oxide also acts as a dispersion strengthening agent on scandia-stabilized zirconia ceramics, and as a result, imparts excellent high temperature strength and strength durability.
【００２３】まず本発明では、スカンジアで安定化され
たジルコニアを対象とするもので、一般的なスカンジア
の添加量は３モル％以上、１５モル％以下である。即ち
スカンジアの含有量が３モル％未満では、セラミックス
の結晶構造に単斜晶の割合が多くなり、ジルコニアの安
定化が不十分となって満足のいく強度が得られ難くな
る。一方、スカンジアによる安定化効果は約１５モル％
で飽和し、高価なスカンジアをそれ以上に含有させるこ
とは、経済的不利益を被るだけである。First, the present invention is intended for scandia-stabilized zirconia, and the general scandia addition amount is 3 mol% or more and 15 mol% or less. That is, if the scandia content is less than 3 mol%, the proportion of monoclinic crystals in the crystal structure of the ceramics increases, and the stabilization of zirconia becomes insufficient, and it becomes difficult to obtain satisfactory strength. On the other hand, the stabilizing effect of scandia is about 15 mol%
Saturating with and containing more expensive scandia only incurs an economic penalty.
【００２４】高温耐久強度と常温でのハンドリング強度
を高める上では、正方晶系を主体とする結晶構造を有す
るものであることが好ましく、そのための好ましいスカ
ンジアの量は３モル％以上、９モル％以下、更に好まし
くは３．５モル％以上、６モル％以下、更に好ましくは
５モル％以下である。In order to enhance the high temperature durability and the handling strength at room temperature, it is preferable to have a crystal structure mainly composed of a tetragonal system, and the preferable scandia content therefor is 3 mol% or more and 9 mol% or more. It is preferably 3.5 mol% or more and 6 mol% or less, more preferably 5 mol% or less.
【００２５】また本発明においては、機械的強度と共に
導電率の経時変化を抑えるため、４Ａ族、５Ａ族、７Ａ
族および４Ｂ族元素の酸化物よりなる群から選択される
少なくとも１種を、スカンジア安定化ジルコニアに対し
０．０１質量％以上、５質量％以下含有させることが必
要となる。Further, in the present invention, in order to suppress the change with time of the electrical conductivity as well as the mechanical strength, 4A group, 5A group, 7A
It is necessary that at least one selected from the group consisting of oxides of Group 4 and Group 4B elements be contained in an amount of 0.01% by mass or more and 5% by mass or less with respect to scandia-stabilized zirconia.
【００２６】ここで、４Ａ族、５Ａ族、７Ａ族および４
Ｂ族元素とは、例えば、理化学辞典第５版（岩波書店：
１９９８年４月２４日発行）に記載されている元素の周
期表（短周期型）に示されている族のことであり、具体
的には、４Ａ族元素の酸化物としてはＴｉＯ2；５Ａ族
元素の酸化物としてはＶ2Ｏ5、Ｎｂ2Ｏ5、Ｔａ2Ｏ5；７
Ａ族元素の酸化物としてはＭｎＯ2；４Ｂ族元素の酸化
物としてはＧｅＯ2が好適である。Here, 4A group, 5A group, 7A group and 4 group
The group B element is, for example, the physics and chemistry dictionary fifth edition (Iwanami Shoten:
(Published on April 24, 1998), which is a group shown in the periodic table (short period type) of elements, specifically, as an oxide of a 4A group element, TiO 2 ; 5A As oxides of group elements, V 2 O 5 , Nb 2 O 5 , Ta 2 O 5 ; 7
The oxide of the A group element MnO 2; As the oxide of the Group 4B elements GeO 2 are preferred.
【００２７】特に、スカンジア安定化ジルコニアの導電
率の初期劣化を抑制すると共に、焼結性を高めてその結
晶構造を安定化させるには、ＴｉＯ2、Ｎｂ2Ｏ5、Ｔａ2
Ｏ5およびＭｎＯ2よりなる群から選択される少なくとも
１種を選択することが望ましい。In particular, in order to suppress the initial deterioration of the electrical conductivity of scandia-stabilized zirconia and to enhance the sinterability and stabilize its crystal structure, TiO 2 , Nb 2 O 5 and Ta 2 are used.
It is desirable to select at least one selected from the group consisting of O 5 and MnO 2 .
【００２８】上記金属酸化物の効果を有効に発揮させる
には、スカンジアで安定化されたジルコニアの総量、具
体的には、ジルコニア分とスカンジア分の合計量に対
し、０．０１質量％以上、５．０質量％以下の範囲で含
有させるのがよく、より好ましくは０．１質量％以上、
３．０質量％以下、更に好ましくは０．３質量％以上、
２．０質量％以下の範囲である。In order to effectively bring out the effect of the above metal oxide, 0.01% by mass or more based on the total amount of zirconia stabilized by scandia, specifically, the total amount of zirconia and scandia components, The content is preferably 5.0% by mass or less, more preferably 0.1% by mass or more,
3.0 mass% or less, more preferably 0.3 mass% or more,
It is within a range of 2.0 mass% or less.
【００２９】上記金属酸化物の含有量が０．０１質量％
を下回る場合は、前述した作用効果が有効に発揮され
ず、逆に５質量％を上回る場合は、初期導電率を低下さ
せる原因になるので好ましくない。The content of the above metal oxide is 0.01% by mass.
If it is less than 5% by weight, the above-mentioned effects are not effectively exhibited. On the contrary, if it exceeds 5% by mass, it may cause a decrease in initial conductivity, which is not preferable.
【００３０】更に本発明においては、不純物として混入
してくる恐れのある酸化ケイ素、および／またはＮａ，
Ｋ，Ｒｂ，Ｃｓの如きアルカリ金属の酸化物の含有量を
極力少なく抑えることが望ましく、好ましくは何れも
０．１質量％以下、より好ましくは０．０５質量％以下
に抑えることが好ましい。Further, in the present invention, silicon oxide and / or Na, which may be mixed as impurities,
It is desirable to minimize the content of alkali metal oxides such as K, Rb, and Cs, preferably 0.1 mass% or less, and more preferably 0.05 mass% or less.
【００３１】上記酸化ケイ素やアルカリ金属酸化物類
は、ジルコニアや前記酸化物に比べると低融点の溶融型
酸化物であり、高温に長時間曝されるとスカンジア安定
化ジルコニア中の粒界付近に偏析して導電率を低下させ
る恐れがあるからである。The above silicon oxide and alkali metal oxides are molten oxides having a lower melting point than zirconia and the above oxides, and when exposed to a high temperature for a long time, they are formed in the vicinity of grain boundaries in scandia-stabilized zirconia. This is because there is a risk of segregation and a decrease in conductivity.
【００３２】従って本発明の燃料電池用スカンジア安定
化ジルコニア電解質中には、酸化ケイ素および／または
アルカリ金属酸化物が実質的に含まれていないことが望
ましいが、何れもジルコニア原料粉末中に不可避的に混
入してくる成分であり、より好ましくは酸化ケイ素の含
有量は０．０３質量％以下、アルカリ金属酸化物の合計
含有量は０．０１質量％以下に抑えることが望ましい。Therefore, it is desirable that the scandia-stabilized zirconia electrolyte for a fuel cell of the present invention does not substantially contain silicon oxide and / or alkali metal oxide, but both are unavoidable in the zirconia raw material powder. It is desirable that the content of silicon oxide be 0.03 mass% or less and the total content of alkali metal oxides be 0.01 mass% or less.
【００３３】ここでアルカリ金属酸化物の合計量とは、
Ｎａ2Ｏ，Ｋ2Ｏ，Ｒｂ2Ｏ，Ｃｓ2Ｏとしたときの各酸化
物の合計量を言う。Here, the total amount of alkali metal oxides means
The total amount of each oxide when Na 2 O, K 2 O, Rb 2 O, and Cs 2 O is used.
【００３４】本発明でいう導電率とは、固体酸化物型燃
料電池用の電解質膜として用いられるセラミックから、
導電率測定用サンプルとしてダイヤモンドカッターで一
部切り出されたテストピースを使用し、直流４端子法で
測定した値をいい、最初から導電率測定用サンプルとし
て作製されたテストピースを用いた値ではない。尚、こ
の測定に用いたテストピースの大きさは、長さ５０ｍ
ｍ、幅５ｍｍで厚さ０．０１〜０．６ｍｍとした。The term "conductivity" as used in the present invention refers to a ceramic used as an electrolyte membrane for a solid oxide fuel cell,
A value measured by the DC 4-terminal method using a test piece partially cut out with a diamond cutter as a sample for conductivity measurement, and not the value using a test piece prepared from the beginning as a sample for conductivity measurement. . The size of the test piece used for this measurement is 50 m in length.
The width was 5 mm and the thickness was 0.01 to 0.6 mm.
【００３５】次に、本発明の燃料電池用スカンジア安定
化ジルコニア電解質においては、その結晶構造が立方晶
を主体とするものである場合、そのグレイン粒子径で平
均径が１μｍ以上、３μｍ以下、最大径が４μｍ以上、
８μｍ以下で、その変動係数が３５％以下であること
が、導電率の経時変化を抑えると共に高レベルの強度を
確保する上で好ましい。Next, in the scandia-stabilized zirconia electrolyte for fuel cells of the present invention, when the crystal structure is mainly cubic, the average grain size of the grains is 1 μm or more and 3 μm or less, and maximum. Diameter is 4 μm or more,
It is preferable that the coefficient of variation is 8 μm or less and the coefficient of variation is 35% or less in order to suppress a change in conductivity over time and to secure a high level of strength.
【００３６】また、その結晶構造が正方晶を主体とする
ものの場合は、そのグレイン粒子径で平均径が０．１μ
ｍ以上、０．５μｍ以下、最大径が０．５μｍ以上、
１．０μｍ以下で、その変動係数が３０％以下であるこ
とが、導電率の経時変化を抑えると共に高温強度耐久性
を確保する上で好ましい。When the crystal structure is mainly tetragonal, the average grain diameter is 0.1 μm.
m or more, 0.5 μm or less, maximum diameter is 0.5 μm or more,
It is preferable that the coefficient of variation is 1.0 μm or less and the coefficient of variation is 30% or less in order to suppress a change in conductivity with time and to secure high temperature strength durability.
【００３７】グレイン粒子径の変動係数が、立方晶の場
合で３５％を上回り、あるいは正方晶の場合で３０％を
上回るものでは、導電率の経時変化が大きくなると共
に、ワイブル係数が１０以下に低下する傾向が生じてく
る。なおワイブル係数とは、強度バラツキの度合いを反
映する材料定数とみなされ、燃料電池用の固体電解質と
して使用するには、ワイブル係数で１０以上、より好ま
しくは１２以上、更に好ましくは１５以上とすることに
よって、素材としての信頼性が高められ、発電システム
の設計も容易となる。一方この値が１０以下のものは、
強度バラツキが大きくて材料としての信頼性を欠き、実
用にそぐわなくなる。When the variation coefficient of grain particle size is more than 35% in the case of cubic crystal or more than 30% in the case of tetragonal crystal, the change with time of conductivity becomes large and the Weibull coefficient becomes 10 or less. It tends to decrease. The Weibull coefficient is regarded as a material constant that reflects the degree of strength variation, and for use as a solid electrolyte for a fuel cell, the Weibull coefficient is 10 or more, more preferably 12 or more, and further preferably 15 or more. As a result, the reliability of the material is increased and the design of the power generation system becomes easier. On the other hand, if this value is 10 or less,
The strength is so large that it lacks reliability as a material, making it unsuitable for practical use.
【００３８】ここで、上記スカンジア安定化ジルコニア
セラミックスのグレイン粒子径は、その表面を走査型電
子顕微鏡で写真撮影し（１０，０００〜２０，０００
倍）、写真視野内の全グレイン粒子の大きさをノギスで
測定した値を元に、個々のデータを集計して求めた平均
径、最大径および変動係数をいう。なお、グレイン粒子
径をノギスで測定する際に、写真視野の端縁に位置する
グレイン粒子で粒子全体が現れていないものは測定対象
から外し、また、縦・横方向の寸法の異なるグレイン粒
子については、その長径と短径の平均値をその粒子径と
した。Here, the grain diameter of the scandia-stabilized zirconia ceramics is photographed on the surface thereof with a scanning electron microscope (10,000 to 20,000).
), The average diameter, maximum diameter and coefficient of variation obtained by collecting individual data based on the value of the size of all grain particles in the photographic field measured with a caliper. When measuring the grain particle size with a caliper, those grain particles located at the edges of the photographic field that do not show the entire particle are excluded from the measurement target, and also for grain particles with different vertical and horizontal dimensions. The average value of the major axis and the minor axis was defined as the particle diameter.
【００３９】また本発明で言う強度とは、ＪｌＳ Ｒ１
６０１の規定に準拠し、導電率測定用のテストピースと
同様にして作製したテストピースを用いて測定した３点
曲げ強度を言い、高温耐久性とは、９５０℃で１０００
時間以上保持した後に測定した強度の経時変化の小さい
ものを言う。The strength referred to in the present invention means JlS R1.
In accordance with the provisions of 601, the three-point bending strength measured using a test piece prepared in the same manner as the test piece for measuring conductivity, high temperature durability is 1000 at 950 ° C.
It refers to a material that has a small change in strength over time after being held for a period of time or more.
【００４０】この様に本発明の燃料電池用スカンジア安
定化ジルコニア電解質は、添加物として４Ａ族、５Ａ
族、７Ａ族および４Ｂ族元素の酸化物よりなる群から選
択される少なくとも１種を、スカンジア安定化ジルコニ
アに対し０．０１〜５質量％添加することで、スカンジ
ア安定化ジルコニア電解質の導電率の経時変化が抑えら
れると共に、常温強度や高温強度およびその耐久性にお
いて一層優れたものとなるので、固体酸化物型燃料電池
の固体電解質として極めて有用なものとなる。As described above, the scandia-stabilized zirconia electrolyte for a fuel cell of the present invention contains the Group 4A and 5A additives as additives.
Of the conductivity of the scandia-stabilized zirconia electrolyte by adding 0.01 to 5% by mass to scandia-stabilized zirconia, of at least one selected from the group consisting of oxides of Group 7, 7A and 4B elements. Since the change over time is suppressed and the strength at room temperature, the strength at high temperature, and the durability thereof are further improved, it is extremely useful as a solid electrolyte of a solid oxide fuel cell.
【００４１】中でも、前記酸化物としてＴｉＯ2，Ｎｂ2
Ｏ3、Ｔａ2Ｏ5およびＭｎＯ2から選択される少なくとも
１種を使用した本発明のスカンジア安定化ジルコニア電
解質は、それらの酸化物が含まれていないものに比べて
初期導電率の低下率が非常に小さく、導電率の経時安定
性にも優れているので、例えば０．０１〜０．６ｍｍ程
度の薄膜シート状とすることにより、燃料電池の固体電
解質膜として極めて優れた性能を発揮する。Above all, as the oxide, TiO 2 , Nb 2
The scandia-stabilized zirconia electrolyte of the present invention using at least one selected from O 3 , Ta 2 O 5 and MnO 2 has a lower rate of decrease in initial conductivity than those containing no oxide thereof. Since it is very small and has excellent stability of conductivity over time, for example, by forming a thin film sheet having a thickness of about 0.01 to 0.6 mm, a very excellent performance as a solid electrolyte membrane of a fuel cell is exhibited.
【００４２】こうした優れた特性を有する本発明に係る
燃料電池用スカンジア安定化ジルコニア電解質の原料と
なる粉末は、市販のスカンジア安定化ジルコニア粉末に
前記特定元素の酸化物粉末をそのまま添加混合して原料
粉末としてもよいし、アルコキシドや硝酸塩、炭酸塩な
どの水溶液等の形で市販ジルコニア粉末に添加し、必要
によっては更に他の添加物などと共に配合し、加水分解
・濾過・洗浄・仮焼・混合粉砕などの処理を施して原料
粉末としてもよい。The powder which is the raw material of the scandia-stabilized zirconia electrolyte for fuel cells according to the present invention having such excellent characteristics is a raw material obtained by adding and mixing the oxide powder of the specific element as it is to the commercially available scandia-stabilized zirconia powder. Powder may be used, or it may be added to commercially available zirconia powder in the form of an aqueous solution of alkoxide, nitrate, carbonate, etc., and, if necessary, further compounded with other additives, etc. for hydrolysis, filtration, washing, calcination, and mixing. The raw material powder may be processed by crushing or the like.
【００４３】この原料粉末の粉体としての好ましい粒度
構成は、平均粒子径が０．３〜３μｍ、好ましくは０．
５〜１．５μｍで、比表面積は３〜３０ｍ2／ｇ、好ま
しくは５〜１５ｍ2／ｇである。A preferred particle size composition of this raw material powder is a powder having an average particle size of 0.3 to 3 μm, preferably 0.1.
The specific surface area is 5 to 1.5 μm and the specific surface area is 3 to 30 m 2 / g, preferably 5 to 15 m 2 / g.
【００４４】特に、混合粉砕後さらに噴霧乾燥してから
造粒し、１０〜１００μｍ程度の顆粒状とした原料粉末
は、その後に成形・焼成したセラミックスとしての密度
を理論密度の９７％以上、好ましくは９８％以上に高め
るのに好適である。In particular, the raw material powder which has been mixed and pulverized, further spray-dried, and then granulated to form granules of about 10 to 100 μm has a density as the ceramics molded and fired thereafter of 97% or more of the theoretical density, preferably Is suitable for increasing to 98% or more.
【００４５】噴霧乾燥する場合は、上記粉砕混合したジ
ルコニア粉末をそのままスプレードライ等により噴霧乾
燥してもよいが、噴霧乾燥する際にバインダー成分
（Ａ）を添加し、それを噴霧乾燥してバインダーを含む
顆粒状としたものを原料粉末として使用すれば、成形性
や焼結性を更に高めることができるので好ましい。In the case of spray-drying, the pulverized and mixed zirconia powder may be spray-dried as it is, but when the spray-drying is performed, the binder component (A) is added and the binder is spray-dried. It is preferable to use a granular material containing the above as a raw material powder because the moldability and sinterability can be further improved.
【００４６】ここで用いられるバインダー（Ａ）の種類
に格段の制限はないが、水溶性のものが好ましく、従来
から知られた有機質もしくは無機質のバインダーを適宜
選択して使用できる。上記バインダー（Ａ）のうち、有
機質バインダーの具体例としては、例えばエチレン系共
重合体、スチレン系共重合体、アクリレート系及びメタ
クリレート系共重合体、酢酸ビニル系共重合体、マレイ
ン酸系共重合体、ビニルブチラール系樹脂、ビニルアセ
タール系樹脂、ビニルホルマール系樹脂、ビニルアルコ
ール系樹脂、ワックス類、エチルセルロース等のセルロ
ース類が例示される。また、無機質バインダーの具体例
としては、ジルコニアゾル、チタニアゾル等が例示され
る。これらのバインダーは、単独で使用し得る他、必要
により２種以上を混合して使用することも勿論可能であ
る。The kind of the binder (A) used here is not particularly limited, but a water-soluble binder is preferable, and conventionally known organic or inorganic binders can be appropriately selected and used. Among the above binders (A), specific examples of organic binders include, for example, ethylene-based copolymers, styrene-based copolymers, acrylate-based and methacrylate-based copolymers, vinyl acetate-based copolymers, maleic acid-based copolymers. Examples thereof include coalesce, vinyl butyral resin, vinyl acetal resin, vinyl formal resin, vinyl alcohol resin, waxes, and celluloses such as ethyl cellulose. Specific examples of the inorganic binder include zirconia sol and titania sol. These binders may be used alone or, if necessary, may be used in combination of two or more kinds.
【００４７】該バインダー（Ａ）の好ましい配合量は、
スカンジア安定化ジルコニア粉末と前記添加酸化物との
合計１００質量部に対し、バインダーの固形分換算で
０．５質量部以上、１０質量部以下、より好ましくは１
質量部以上、５質量部以下である。この様にして調製さ
れたジルコニア粉末を含む顆粒状の原料粉末は、プレス
成形用原料として好適に使用される。The preferred blending amount of the binder (A) is
0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass in terms of solid content of the binder, based on 100 parts by mass of the scandia-stabilized zirconia powder and the added oxide.
It is not less than 5 parts by mass and not more than parts by mass. The granular raw material powder containing the zirconia powder thus prepared is preferably used as a raw material for press molding.
【００４８】本発明に係る燃料電池用のスカンジア安定
化ジルコニア電解質の製法は特に制限されず、上記の様
にして調製したスカンジア安定化ジルコニア粉末を使用
し、金型やラバーを用いたプレス成形法、押出成形法、
ドクターブレードによるシート成形法、支持基体へのス
ラリーコート法や蒸着法等によって成膜し、焼成する方
法が採用される。The method for producing the scandia-stabilized zirconia electrolyte for the fuel cell according to the present invention is not particularly limited, and the scandia-stabilized zirconia powder prepared as described above is used, and a press molding method using a mold or rubber is used. , Extrusion molding method,
A method of forming a film by a sheet forming method using a doctor blade, a slurry coating method on a supporting substrate, a vapor deposition method, or the like, and firing is adopted.
【００４９】特に１０〜２００μｍの薄膜シート状物を
製造するには、ドクターブレード法によるシート成形が
好適であり、前述した特定の酸化物が配合されたスカン
ジア安定化ジルコニア原料粉末とバインダー（Ｂ）およ
び分散媒からなるスラリーをキャリアフィルム上に敷き
延べてシート状に成形し、これを乾燥し分散媒を揮発さ
せることによってグリーンシートを得、これを切断、パ
ンチング等により適当な寸法に揃えてから焼成すればよ
い。Particularly, in order to manufacture a thin film sheet having a thickness of 10 to 200 μm, the sheet molding by the doctor blade method is suitable, and the scandia-stabilized zirconia raw material powder and the binder (B) containing the above-mentioned specific oxide are suitable. And a slurry consisting of a dispersion medium is spread on a carrier film to form a sheet, which is dried to volatilize the dispersion medium to obtain a green sheet, which is cut and punched to obtain an appropriate size. It may be fired.
【００５０】焼成は、上記の様な方法で成形したグリー
ンシートあるいはスラリーコート体を棚板や多孔質セッ
ター上に載置し、１３００〜１６００℃、好ましくは１
３５０〜１５００℃程度、最も一般的には１４００〜１
４５０℃で１〜５時間程度加熱することによって行なわ
れる。The firing is carried out by placing the green sheet or slurry-coated body molded by the above-mentioned method on a shelf plate or a porous setter at 1300 to 1600 ° C., preferably 1
350-1500 ° C, most commonly 1400-1
It is carried out by heating at 450 ° C. for about 1 to 5 hours.
【００５１】シート状の該ジルコニアセラミックスは、
高度の熱的、機械的、電気的、化学的特性を有してお
り、燃料電池の固体電解質膜用として実用化する場合
は、要求強度を満たしつつ通電ロスを可及的に抑えるた
め、シート厚さを０．０１ｍｍ以上、より好ましくは
０．０２ｍｍ以上で、０．６ｍｍ以下、より好ましくは
０．３ｍｍ以下、更に好ましくは０．２ｍｍ以下とする
のが良い。The sheet-shaped zirconia ceramic is
It has a high level of thermal, mechanical, electrical, and chemical properties, and when it is put to practical use for a solid electrolyte membrane of a fuel cell, it is a sheet to satisfy the required strength and suppress the conduction loss as much as possible. The thickness is preferably 0.01 mm or more, more preferably 0.02 mm or more and 0.6 mm or less, more preferably 0.3 mm or less, and further preferably 0.2 mm or less.
【００５２】大きさは特に制限されないが、実用規模で
十分な発電容量の燃料電池システムを得るには、５０ｃ
ｍ2以上、好ましくは１００ｃｍ2以上の寸法とすること
が望ましい。The size is not particularly limited, but in order to obtain a fuel cell system having a sufficient power generation capacity on a practical scale, 50 c
It is desirable that the size is m 2 or more, preferably 100 cm 2 or more.
【００５３】またシートの形状は、正方形や長方形、円
盤状、もしくは中央部に穴が形成されたドーナツ状が一
般的であるが、これらに限定される理由はなく、他の任
意の多角形状や穴明き多角形状など、どの様な形状であ
っても構わない。またシート形状以外にも、円筒状や一
方が封じられた円筒状、ハニカム状、コルゲート状やデ
ィンプル状の如き３次元形状のものでも有効に使用でき
る。The sheet is generally in the shape of a square, a rectangle, a disc, or a donut with a hole formed in the center, but there is no reason to be limited to these, and any other polygonal shape or Any shape such as a perforated polygonal shape may be used. Besides the sheet shape, a three-dimensional shape such as a cylindrical shape, a cylindrical shape with one side sealed, a honeycomb shape, a corrugated shape or a dimple shape can be effectively used.
【００５４】上記スラリーに配合されるバインダー
（Ｂ）の種類にも格別の制限はなく、従来から知られた
有機質もしくは無機質のバインダーを適宜選択して使用
することができる。有機質バインダーとしては、例えば
エチレン系共重合体、スチレン系共重合体、アクリレー
ト系及びメタクリレート系共重合体、酢酸ビニル系共重
合体、マレイン酸系共重合体、ビニルブチラール系樹
脂、ビニルアセタール系樹脂、ビニルホルマール系樹
脂、ビニルアルコール系樹脂、ワックス類、エチルセル
ロース等のセルロース類等が例示される。There is no particular limitation on the kind of the binder (B) blended in the slurry, and conventionally known organic or inorganic binders can be appropriately selected and used. Examples of the organic binder include ethylene-based copolymers, styrene-based copolymers, acrylate-based and methacrylate-based copolymers, vinyl acetate-based copolymers, maleic acid-based copolymers, vinyl butyral-based resins, vinyl acetal-based resins. , Vinyl formal resin, vinyl alcohol resin, waxes, celluloses such as ethyl cellulose, and the like.
【００５５】これらの中でも未焼成ジルコニア系成形体
を得る際の成形性や強度、焼成時の熱分解性等の点か
ら、メチルアクリレート、エチルアクリレート、プロピ
ルアクリレート、ブチルアクリレート、イソブチルアク
リレート、シクロヘキシルアクリレート、２−エチルヘ
キシルアクリレート等の炭素数１０以下のアルキル基を
有するアルキルアクリレート類；メチルメタクリレー
ト、エチルメタクリレート、ブチルメタクリレート、イ
ソブチルメタクリレート、オクチルメタクリレート、２
−エチルヘキシルメタクリレート、デシルメタクリレー
ト、ドデシルメタクリレート、ラウリルメタクリレー
ト、シクロヘキシルメタクリレート等の炭素数２０以下
のアルキル基を有するアルキルメタクリレート類；ヒド
ロキシエチルアクリレート、ヒドロキシプロピルアクリ
レート、ヒドロキシエチルメタクリレート、ヒドロキシ
プロピルメタクリレート等のヒドロキシアルキル基を有
するヒドロキシアルキルアクリレートまたはヒドロキシ
アルキルメタクリレート類；ジメチルアミノエチルアク
リレート、ジメチルアミノエチルメタクリレート等のア
ミノアルキルアクリレートまたはアミノアルキルメタク
リレート類；（メタ）アクリル酸、マレイン酸、モノイ
ソプロピルマレートの如きマレイン酸半エステル等のカ
ルボキシル基含有モノマー；などの少なくとも１種を重
合または共重合させることによって得られる、数平均分
子量が２０，０００〜２００，０００、より好ましくは
５０，０００〜１００，０００の（メタ）アクリレート
系共重合体が好ましいものとして推奨される。Among these, from the viewpoints of moldability and strength in obtaining an unsintered zirconia-based compact, thermal decomposability during sintering, etc., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, Alkyl acrylates having an alkyl group having 10 or less carbon atoms such as 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, 2
-Alkyl methacrylates having an alkyl group having 20 or less carbon atoms such as ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate; hydroxyalkyl groups such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate Hydroxyalkyl acrylates or hydroxyalkyl methacrylates having amino groups; aminoalkyl acrylates or aminoalkyl methacrylates such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; maleic acid half esters such as (meth) acrylic acid, maleic acid and monoisopropyl maleate Carboxyl group-containing models such as A (meth) acrylate-based copolymer having a number average molecular weight of 20,000 to 200,000, more preferably 50,000 to 100,000, obtained by polymerizing or copolymerizing at least one of Recommended as preferred.
【００５６】これらの有機質バインダーは、単独で使用
し得る他、必要により２種以上を適宜組み合わせて使用
することができる。特に好ましいのはイソブチルメタク
リレートおよび／または２−エチルヘキシルメタクリレ
ートを６０質量％以上含むモノマーの重合体である。These organic binders can be used alone or in combination of two or more kinds, if necessary. Particularly preferred is a polymer of a monomer containing 60% by mass or more of isobutyl methacrylate and / or 2-ethylhexyl methacrylate.
【００５７】また無機質バインダーとしては、ジルコニ
アゾル、シリカゾル、チタニアゾル等が単独で若しくは
２種以上組み合わせて使用できる。As the inorganic binder, zirconia sol, silica sol, titania sol or the like can be used alone or in combination of two or more kinds.
【００５８】ジルコニア系原料粉末とバインダーの使用
比率は、前者１００質量部に対して後者が固形分換算で
５〜３０質量部、より好ましくは１０〜２０質量部の範
囲が好適であり、バインダーの使用量が不足する場合
は、成形体の強度や柔軟性が不十分となり、逆に多過ぎ
ると、スラリーの粘度調節が困難になるばかりでなく、
焼成時のバインダー成分の分解放出が多く且つ激しくな
って均質な焼結体が得られ難くなる。The ratio of the zirconia-based raw material powder to the binder used is preferably 5 to 30 parts by mass, more preferably 10 to 20 parts by mass in terms of solid content, based on 100 parts by mass of the former. If the amount used is insufficient, the strength and flexibility of the molded article will be insufficient, and conversely, if it is too large, not only will it be difficult to control the viscosity of the slurry,
The decomposition and release of the binder component during firing are large and intense, making it difficult to obtain a homogeneous sintered body.
【００５９】この様にして得られたジルコニア粉末を含
むスラリーは、ドクターブレード法によって好適にシー
ト成形することができる。The slurry containing the zirconia powder thus obtained can be suitably formed into a sheet by the doctor blade method.
【００６０】また未焼成ジルコニア成形体の製造に使用
される溶媒としては、水；メタノール、エタノール、２
−プロパノール、１−ブタノール、１−ヘキサノール等
のアルコール類；アセトン、２−ブタノン等のケトン
類；ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素
類；ベンゼン、トルエン、キシレン、エチルベンゼン等
の芳香族炭化水素類；酢酸メチル、酢酸エチル、酢酸ブ
チル等の酢酸エステル類等が適宜選択して使用される。
これらの溶媒も単独で使用し得る他、２種以上を適宜混
合して使用することができる。これら溶媒の使用量は、
グリーンシート成形時におけるスラリーの粘度を加味し
て適当に調節すればよいが、好ましくはスラリー粘度が
１〜１０Ｐａ・ｓ、より好ましくは２〜５Ｐａ・ｓの範
囲となる様に調整するのがよい。The solvent used in the production of the green zirconia compact is water; methanol, ethanol, 2
-Alcohols such as propanol, 1-butanol and 1-hexanol; Ketones such as acetone and 2-butanone; Aliphatic hydrocarbons such as pentane, hexane and heptane; Aromatic carbonization such as benzene, toluene, xylene and ethylbenzene Hydrogen; acetic acid esters such as methyl acetate, ethyl acetate, butyl acetate, etc. are appropriately selected and used.
These solvents may be used alone, or two or more kinds may be appropriately mixed and used. The amount of these solvents used is
It may be appropriately adjusted in consideration of the viscosity of the slurry at the time of forming the green sheet, but it is preferable to adjust the slurry viscosity to be in the range of 1 to 10 Pa · s, and more preferably 2 to 5 Pa · s. .
【００６１】上記スラリーの調製に当たっては、ジルコ
ニア系原料粉末の解膠や分散を促進するため、ポリアク
リル酸、ポリアクリル酸アンモニウム等の高分子電解
質；クエン酸、酒石酸等の有機酸；イソブチレンまたは
スチレンと無水マレイン酸との共重合体およびそのアン
モニウム塩あるいはアミン塩、ブタジエンと無水マレイ
ン酸との共重合体およびそのアンモニウム塩等の分散
剤；未焼成成形体（グリーンシート）に柔軟性を付与す
るためのフタル酸ジブチル、フタル酸ジオクチル等のフ
タル酸エステル類、プロピレングリコール等のグリコー
ル類やグリコールエーテル類などの可塑剤；更には界面
活性剤や消泡剤などを必要に応じて添加することができ
る。In the preparation of the above slurry, in order to accelerate the deflocculation and dispersion of the zirconia-based raw material powder, a polyelectrolyte such as polyacrylic acid or ammonium polyacrylate; an organic acid such as citric acid or tartaric acid; isobutylene or styrene. And maleic anhydride copolymers and their ammonium salts or amine salts, butadiene and maleic anhydride copolymers and their ammonium salts, and other dispersants; give flexibility to the green body (green sheet) Phthalates such as dibutyl phthalate and dioctyl phthalate, plasticizers such as glycols and glycol ethers such as propylene glycol; and surfactants and antifoaming agents may be added as necessary. it can.
【００６２】上記原料配合からなるスラリーを前述の様
な方法で成形し、乾燥してジルコニア系グリーン体を得
た後、これを加熱焼成することによって本発明のスカン
ジア安定化ジルコニア電解質を得る。A slurry composed of the above raw materials is molded by the above-mentioned method and dried to obtain a zirconia-based green body, which is then heated and calcined to obtain the scandia-stabilized zirconia electrolyte of the present invention.
【００６３】この焼成工程では、反りやうねり等の変形
を生じることなく平坦度の高い薄肉シート状の焼結体を
得るための手段として、該グリーンシート以上の面積を
有し、ＪＩＳ Ｋ７１２５（１９８７）で規定されてい
る「プラスチックフィルムおよびシートの摩擦係数試験
方法」に準拠して測定される静摩擦係数が１．５以下
で、通気性が０．０００５m/s・kPa以上である多孔質シ
ートの間に、前記グリーンシートを、その周縁がはみ出
さない様に挟み込んで焼成し、あるいは上記多孔質シー
トを前記グリーンシートの周縁がはみ出さない様に載せ
てから焼成を行なうことが望ましい。In this firing step, JIS K7125 (1987) has an area larger than that of the green sheet as a means for obtaining a thin sheet-like sintered body having high flatness without deformation such as warping or waviness. Of a porous sheet having a static friction coefficient of 1.5 or less and a breathability of 0.0005 m / s · kPa or more, which is measured according to the “method for testing friction coefficient of plastic film and sheet” It is desirable that the green sheet be sandwiched between the green sheets so that the peripheral edges thereof do not protrude, and then baked, or that the porous sheet is placed so that the peripheral edges of the green sheet do not protrude.
【００６４】[0064]
【実施例】以下、実施例及び比較例を挙げて本発明をよ
り具体的に説明するが、本発明はもとより下記実施例に
よって制限を受けるものではなく、前・後記の趣旨に適
合し得る範囲で適当に変更して実施することも可能であ
り、それらはいずれも本発明の技術的範囲に包含され
る。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples, and is within a range applicable to the gist of the preceding and the following. It is also possible to carry out by appropriately changing the above, and all of them are included in the technical scope of the present invention.
【００６５】実施例１
４．５モル％スカンジア部分安定化ジルコニア粉末（第
一稀元素化学社製：商品名「４．５ＳｃＳＺ」）１００
質量部に、イソプロピルアルコール６０質量部にチタニ
ウムイソプロポキシドを酸化チタン換算で０．３質量部
となる様に添加した混合物を加え、ロータリーエバポレ
ーターでイソプロピルアルコールを減圧留去した後、さ
らに減圧乾燥してから８００℃で仮焼し、酸化チタンが
０．３質量％分散した４．５モル％スカンジア部分安定
化ジルコニア粉末（Ａ）を得た。該粉末中のシリカ含量
は０．００４質量％、酸化ナトリウム含量は０．００１
質量％であった。Example 1 100% 4.5 mol% scandia partially stabilized zirconia powder (manufactured by Daiichi Rare Element Chemical Co., Ltd .: trade name "4.5ScSZ") 100
To 60 parts by mass of isopropyl alcohol, a mixture of 60 parts by mass of isopropyl alcohol and 0.3 part by mass of titanium isopropoxide in terms of titanium oxide was added, and isopropyl alcohol was distilled off under reduced pressure by a rotary evaporator, followed by further drying under reduced pressure. Then, it was calcined at 800 ° C. to obtain 4.5 mol% scandia partially stabilized zirconia powder (A) in which 0.3% by mass of titanium oxide was dispersed. The silica content in the powder was 0.004% by mass, and the sodium oxide content was 0.001.
It was mass%.
【００６６】この粉末（Ａ）１００質量部に対し、水７
０質量部と、エチルアクリレートを主成分とするアクリ
レート共重合体からなる水溶性バインダー（分子量：５
０，０００、ガラス転移温度：−１４℃）を固形分換算
で５質量部加え、ボールミルで２０時間分散混合した
後、得られたスラリーをスプレードライにより噴霧乾燥
し、バインダー添加０．３質量％酸化チタン分散４．５
モル％スカンジア部分安定化ジルコニア粉末（Ｂ）を得
た。To 100 parts by mass of this powder (A), 7 parts of water was added.
0 parts by mass and a water-soluble binder composed of an acrylate copolymer containing ethyl acrylate as a main component (molecular weight: 5
50,000, glass transition temperature: −14 ° C.) in terms of solid content was added in an amount of 5 parts by mass, and the mixture was dispersed and mixed in a ball mill for 20 hours, and the resulting slurry was spray-dried by spray drying to add 0.3% by mass of a binder. Titanium oxide dispersion 4.5
A mol% scandia partially stabilized zirconia powder (B) was obtained.
【００６７】該ジルコニア粉末（Ｂ）を使用し、ラバー
プレス法により１０００ｋｇ／ｃｍ 2の圧力で板状に成
形した後１４００℃で３時間焼成し、１辺が約５０ｍｍ
角の正方形で、厚さが０．５ｍｍの酸化チタン０．３質
量％を含む燃料電池用の４．５モル％スカンジア部分安
定化ジルコニアシート（I）を得た。このシート焼成体
の密度をアルキメデス法によって求めたところ、理論密
度の９８．８％であった。Using the zirconia powder (B), a rubber
1000 kg / cm by pressing method 2Pressure to form a plate
After shaping, it is baked at 1400 ℃ for 3 hours, and one side is about 50mm
Titanium oxide 0.3 with a square shape and a thickness of 0.5 mm
4.5 mol% scandia partial depletion for fuel cells containing
A stabilized zirconia sheet (I) was obtained. This sheet fired body
The density of is calculated by Archimedes' method,
The degree was 98.8%.
【００６８】また、上記で得たジルコニア粉末（Ａ）１
００質量部を、メタクリル酸エステル共重合体からなる
バインダー（分子量：３０，０００、ガラス転移温度：
−８℃）を固形分換算で１４質量部、可塑剤としてジブ
チルフタレート２質量部、分散媒としてトルエン／イソ
プロピルアルコール（質量比：３／２）の混合溶剤５０
質量部と共に、直径５ｍｍのジルコニアボールが装入さ
れたナイロンポットに入れ、臨界速度の７０％の約６０
ｒｐｍで４０時間混練してスラリーを調製した。Further, the zirconia powder (A) 1 obtained above
A binder (molecular weight: 30,000, glass transition temperature:
-8 ° C.) in terms of solid content, 14 parts by mass, dibutyl phthalate 2 parts by mass as a plasticizer, toluene / isopropyl alcohol (mass ratio: 3/2) mixed solvent 50 as a dispersion medium.
Along with the parts by mass, put it in a nylon pot charged with zirconia balls with a diameter of 5 mm, and make it about 60% of 70% of the critical speed.
A slurry was prepared by kneading at rpm for 40 hours.
【００６９】このスラリーの一部を採取し、トルエン／
イソプロピルアルコール（質量比：３／２）の混合溶剤
で希釈し、島津製作所製のレーザー回折式粒度分布測定
装置「ＳＡＬＤ−１０００」を用いて、スラリー中の固
形成分の粒度分布を測定したところ、平均粒子径（５０
体積％径）が０．４９μｍ、９０体積％径が１．１８μ
ｍ、限界粒子径（１００体積％径）が２．８８μｍであ
った。A part of this slurry was sampled, and toluene /
Diluted with a mixed solvent of isopropyl alcohol (mass ratio: 3/2) and measured the particle size distribution of solid components in the slurry using a laser diffraction particle size distribution analyzer “SALD-1000” manufactured by Shimadzu Corporation. Average particle size (50
Volume% diameter) is 0.49 μm, 90 volume% diameter is 1.18 μm
m, and the limit particle diameter (100% by volume diameter) was 2.88 μm.
【００７０】このスラリーを濃縮脱泡してから粘度を３
Ｐａ・ｓ（２３℃）に調整し、最後に２００メッシュの
フィルターに通してから、ドクターブレード法によりポ
リエチレンテレフタレート（ＰＥＴ）フィルム上に塗工
し、厚さ約０．１８ｍｍのグリーンシートを得た。この
グリーンシートを１辺が約１２５ｍｍの正方形に切断
し、その上下をウネリ最大高さが１０μｍの９９．５％
アルミナ多孔質板で挟んで脱脂した後、１４００℃で３
時間焼成し、１辺が約１００ｍｍ角の正方形で、厚さが
０．１５ｍｍの酸化チタン０．３質量％を含む燃料電池
用の４．５モル％スカンジア部分安定化ジルコニアシー
ト（II）を得た。The slurry was concentrated and defoamed and then the viscosity was reduced to 3
It was adjusted to Pa · s (23 ° C.) and finally passed through a 200 mesh filter, and then applied on a polyethylene terephthalate (PET) film by the doctor blade method to obtain a green sheet having a thickness of about 0.18 mm. . This green sheet is cut into a square with a side of about 125 mm, and the top and bottom of the green sheet are 99.5% with a maximum height of 10 μm.
After degreasing by sandwiching with alumina porous plate, 3 at 1400 ℃
Sintered for an hour to obtain a 4.5 mol% scandia partially stabilized zirconia sheet (II) for a fuel cell, which is a square having a side of about 100 mm and a thickness of 0.15 mm and which contains 0.3% by mass of titanium oxide. It was
【００７１】上記ジルコニアシート（I）と（II）をダ
イヤモンドカッターで幅５ｍｍ、長さ５０ｍｍの短冊状
に切断して導電率測定用と３点曲げ強度測定用のテスト
ピースとし、このテストピースを、９５０℃および７５
０℃に保持した電気炉中に５００時間、１０００時間、
２０００時間および３０００時間曝露した後、導電率と
３点曲げ強度を測定した。The above zirconia sheets (I) and (II) were cut with a diamond cutter into strips each having a width of 5 mm and a length of 50 mm to prepare test pieces for measuring conductivity and 3-point bending strength. , 950 ° C and 75
500 hours, 1000 hours in an electric furnace maintained at 0 ° C
After exposure for 2000 hours and 3000 hours, conductivity and three-point bending strength were measured.
【００７２】導電率の測定は、上記高温に曝露されたテ
ストピースを１ｃｍ間隔で４ヵ所に直径０．２ｍｍの白
金線を巻付け、白金ペーストを塗ってから１００℃で乾
燥・固定して電流・電圧端子とし、白金線がテストピー
スに密着する様に白金線を巻いたテストピースの両端を
アルミナ板で挟み、その上から約５００ｇの荷重をかけ
た状態で、外側の２端子に０．１ｍＡの一定電流を流
し、内側の２端子の電圧をデジタルマルチメーター（ア
ドバンテスト社製：商品名「ＴＲ６８４５型」）を使用
し、直流４端子法で測定した。The electrical conductivity was measured by winding a platinum wire having a diameter of 0.2 mm around the test piece exposed to the high temperature at 1 cm intervals at 4 locations, applying a platinum paste, drying and fixing at 100 ° C., and applying an electric current.・ As a voltage terminal, sandwich both ends of a test piece in which a platinum wire is wound so that the platinum wire adheres to the test piece, sandwich the alumina plate, and apply a load of about 500 g from the top of the test piece. A constant current of 1 mA was applied, and the voltage at the two inner terminals was measured by a DC four-terminal method using a digital multimeter (manufactured by Advantest: trade name "TR6845 type").
【００７３】導電率の耐久安定性は、初期の導電率と所
定時間後の導電率の経時変化を測定し、その比から下記
式によって求めた。
導電率の劣化率＝［（初期導電率−所定時間保持後の導
電率）／（初期導電率）］×１００（％）
曲げ強度の測定は、ＪＩＳ Ｒ１６０１に準拠し、高温
曝露されたテストピースを室温で測定し、初期の曲げ強
度と所定時間後の曲げ強度との比から、下記式によって
求めた。
強度の劣化率＝［（初期強度−所定時間保持後の強度）
／（初期強度）］×１００（％）
更に、得られた燃料電池用のジルコニアシート（Ｉ）と
（II）の組成をＩＣＰ発光分析法によって測定した。結
果を表１に示す。The endurance stability of the electric conductivity was determined by the following equation from the ratio of the initial electric conductivity and the change with time of the electric conductivity after a predetermined time. Deterioration rate of electrical conductivity = [(initial electrical conductivity-electrical conductivity after holding for a predetermined time) / (initial electrical conductivity)] x 100 (%) Bending strength was measured according to JIS R1601, and the test piece exposed to high temperature was used. Was measured at room temperature and calculated from the ratio of the initial bending strength and the bending strength after a predetermined time by the following formula. Deterioration rate of strength = [(initial strength-strength after holding for a predetermined time)
/ (Initial strength)] × 100 (%) Further, the compositions of the obtained fuel cell zirconia sheets (I) and (II) were measured by ICP emission spectrometry. The results are shown in Table 1.
【００７４】実施例２
４．０モル％スカンジア部分安定化ジルコニア粉末（第
一稀元素化学社製：商品名「４ＳｃＳＺ」）１００質量
部に、水６０質量部に酸化ニオブ換算で１．０質量部の
塩化ニオブを加水分解して得た水酸化ニオブと、上記実
施例１で用いたのと同じアクリレート共重合体からなる
水溶性バインダー１質量部を加え、ボールミルで２０分
間分散混合する。次いでスプレードライ法で噴霧乾燥す
ることにより、本発明に係る燃料電池用のバインダー添
加１．０％酸化ニオブ分散４．０モル％スカンジア部分
安定化ジルコニア粉末（Ｃ）を得た。該粉末中のシリカ
含量は０．００５質量％、酸化ナトリウム含量は０．０
０１質量％であった。Example 2 4.0 parts by mass of scandia partially stabilized zirconia powder (manufactured by Daiichi Rare Element Chemical Co., Ltd .: trade name "4ScSZ"), 60 parts by mass of water, and 1.0 part by mass of niobium oxide. Niobium hydroxide obtained by hydrolyzing 1 part of niobium chloride and 1 part by mass of a water-soluble binder composed of the same acrylate copolymer as used in Example 1 above are added and dispersed and mixed in a ball mill for 20 minutes. Then, by spray drying by a spray drying method, a binder-added 1.0% niobium oxide dispersed 4.0 mol% scandia partially stabilized zirconia powder (C) for the fuel cell according to the present invention was obtained. The silica content in the powder was 0.005% by mass, and the sodium oxide content was 0.0.
It was 01% by mass.
【００７５】この粉末（Ｃ）を用いて、前記実施例１と
同様にしてラバープレス法により成形してから焼成し、
１辺が約５０ｍｍ角の正方形で厚さが０．５ｍｍの酸化
ニオブ１．０質量％を含む燃料電池用の４．０モル％ス
カンジア部分安定化ジルコニアシート（III）を得た。
このシート焼成体の密度をアルキメデス法によって求め
たところ、理論密度の９８．１％であった。Using this powder (C), molding was carried out by the rubber press method in the same manner as in Example 1 above, followed by firing,
A 4.0 mol% scandia partially stabilized zirconia sheet (III) for fuel cells containing 1.0% by mass of niobium oxide having a side of about 50 mm square and a thickness of 0.5 mm was obtained.
When the density of this fired sheet was determined by the Archimedes method, it was 98.1% of the theoretical density.
【００７６】このシートを、実施例１と同様にしてテス
トピースを作成し、導電率と３点曲げ強度の耐久安定性
を求めた。結果を表１に示す。A test piece was prepared from this sheet in the same manner as in Example 1 to determine the conductivity and durability stability of three-point bending strength. The results are shown in Table 1.
【００７７】実施例３
スカンジアで安定化されていないジルコニア粉末（住友
大阪セメント社製：商品名「ＯＺＣ−０」）に対して、
酸化スカンジウム粉末（和光純薬工業社製：試薬９９．
９％）を８モル％となる様に添加して混合し、これらの
混合粉末１００質量部に対して更に酸化タンタル粉末
（和光純薬工業社製：試薬９９．８％）を１．５質量％
添加して得た合計２Ｋｇの粉末を、水３Ｋｇと共に０．
５ｍｍ径のジルコニアボールの入ったビーズミル（コト
ブキ技研工業社製：商品名「アペックスミルＡＭ−
１」）に入れて、ローター先端周速度が７ｍ／ｓｅｃで
１時間湿式粉砕した。Example 3 For zirconia powder that was not stabilized with scandia (Sumitomo Osaka Cement Co., Ltd .: trade name "OZC-0"),
Scandium oxide powder (manufactured by Wako Pure Chemical Industries, Ltd .: Reagent 99.
9%) and added so as to be 8 mol% and mixed, and to 100 parts by mass of these mixed powders, 1.5 parts by mass of tantalum oxide powder (manufactured by Wako Pure Chemical Industries, Ltd .: reagent 99.8%). %
A total of 2 Kg of powder obtained by addition was added with 3 Kg of water to give an amount of 0.
Bead mill containing zirconia balls with a diameter of 5 mm (Kotobuki Giken Co., Ltd. product name: Apex Mill AM-
1 "), and wet-milled for 1 hour at a rotor tip peripheral speed of 7 m / sec.
【００７８】得られたスラリーをロータリーエバーポレ
ータに入れ、更に等量のオクタノールを入れ減圧しなが
ら加熱して水を流出させ、オクタノール置換スラリーを
得た。このスラリーを更に減圧下に加熱してオクタノー
ルを流出させた後、減圧乾燥することにより、本発明に
かかる燃料電池用の酸化タンタル１．５質量％分散８．
０モル％スカンジア安定化ジルコニア粉末（Ｄ）を得
た。該粉末中のシリカ含量は０．００４質量％、酸化ナ
トリウム含量は０．００１質量％であった。The obtained slurry was put in a rotary evaporator, and an equal amount of octanol was further put therein and heated under reduced pressure to let water flow out to obtain an octanol-substituted slurry. The slurry was further heated under reduced pressure to allow octanol to flow out, and then dried under reduced pressure to disperse 1.5% by mass of tantalum oxide for a fuel cell according to the present invention.
A 0 mol% scandia-stabilized zirconia powder (D) was obtained. The silica content in the powder was 0.004% by mass, and the sodium oxide content was 0.001% by mass.
【００７９】この粉末（Ｄ）を用いて、１２５０Ｋｇ／
ｃｍ2の圧力で前記実施例１と同様にラバープレス法に
よって成形した後、１４５０℃で焼成し、１辺が約５０
ｍｍ角の正方形で厚さが０．５ｍｍの、酸化タンタル
１．５質量％を含む燃料電池用の８．０モル％スカンジ
ア安定化ジルコニアシート（IV）を得た。このシート焼
成体の密度は、理論密度の９７．２％であった。Using this powder (D), 1250 Kg /
After molding by a rubber press method at a pressure of cm 2 in the same manner as in Example 1, the material is fired at 1450 ° C. and one side is about 50.
A 8.0 mol% scandia-stabilized zirconia sheet (IV) for a fuel cell containing 1.5% by mass of tantalum oxide having a square shape of mm square and a thickness of 0.5 mm was obtained. The density of this sheet fired body was 97.2% of the theoretical density.
【００８０】このシート（IV)を用いて、前記実施例１
と同様にしてテストピースを作成し、導電率と３点曲げ
強度の耐久安定性を求め、表１に示す結果を得た。Using this sheet (IV), the above-mentioned Example 1
A test piece was prepared in the same manner as above, and the conductivity and the durability stability of the three-point bending strength were obtained, and the results shown in Table 1 were obtained.
【００８１】実施例４
４．５モル％スカンジア部分安定化ジルコニア粉末（第
一稀元素化学社製：商品名「４．５ＳｃＳＺ」）１００
質量部に、酸化マンガン換算で０．８質量部の硝酸マン
ガンを溶解した水６０質量部と、前記実施例１で用いた
のと同じ水溶性バインダー１質量部を加え、ボールミル
で２０時間分散した後、スプレードライ法によって噴霧
乾燥し、バインダー添加０．８質量％酸化マンガン分散
４．０モル％スカンジア部分安定化ジルコニア粉末
（Ｅ）を得た。該粉末中のシリカ含量は０．００４質量
％、酸化ナトリウム含量は０．００１質量％であった。Example 4 100% of 4.5 mol% scandia partially stabilized zirconia powder (manufactured by Daiichi Rare Element Chemical Co., Ltd .: trade name "4.5ScSZ") 100
60 parts by mass of water in which 0.8 part by mass of manganese nitrate in terms of manganese oxide was dissolved, and 1 part by mass of the same water-soluble binder as used in Example 1 were added to the parts by mass, and dispersed by a ball mill for 20 hours. Then, it was spray dried by a spray drying method to obtain a binder-added 0.8% by mass manganese oxide dispersion 4.0 mol% scandia partially stabilized zirconia powder (E). The silica content in the powder was 0.004% by mass, and the sodium oxide content was 0.001% by mass.
【００８２】この粉末（Ｅ）を用いて、前記実施例１と
同様にしてラバープレス法により板状に成形してから焼
成し、１辺が約５０ｍｍ角の正方形で、厚さが０．５ｍ
ｍの酸化マンガン０．８質量％を含む燃料電池用の４．
５モル％スカンジア部分安定化ジルコニアシート（Ｖ）
を得た。このシートの密度は、理論密度の９８．４％で
あった。This powder (E) was molded into a plate shape by a rubber pressing method in the same manner as in Example 1, and then fired to form a square having a side of about 50 mm and a thickness of 0.5 m.
3. for a fuel cell containing 0.8% by weight of manganese oxide.
5 mol% scandia partially stabilized zirconia sheet (V)
Got The density of this sheet was 98.4% of the theoretical density.
【００８３】このシートを、実施例１と同様にしてテス
トピースを作成し、導電率と３点曲げ強度の耐久安定性
を求めた。結果を表１に示す。A test piece was prepared from this sheet in the same manner as in Example 1, and the conductivity and durability stability of three-point bending strength were determined. The results are shown in Table 1.
【００８４】比較例１
４．５モル％スカンジア部分安定化ジルコニア粉末（第
一稀元素化学社製：商品名「４．５ＳｃＳＺ」）１００
質量部に対し、水７０質量部と、エチルアクリレートを
主成分とする水溶性アクリレート共重合体からなるバイ
ンダーを固形分換算で５質量部加え、ボールミルで２０
時間分散混合した後、得られたスラリーをスプレードラ
イ法によって噴霧乾燥することにより、バインダー添加
４．５モル％スカンジア部分安定化ジルコニア粉末
（ａ）を得た。Comparative Example 1 4.5 mol% scandia partially stabilized zirconia powder (manufactured by Daiichi Rare Element Chemical Co., Ltd .: trade name "4.5ScSZ") 100
70 parts by weight of water and 5 parts by weight of a binder composed of a water-soluble acrylate copolymer containing ethyl acrylate as a main component in terms of solid content are added to 20 parts by ball mill.
After time-dispersed mixing, the resulting slurry was spray-dried by a spray-drying method to obtain a binder-added 4.5 mol% scandia partially stabilized zirconia powder (a).
【００８５】このジルコニア粉末（ａ）を使用し、ラバ
ープレス法により１０００ｋｇ／ｃｍ2の圧力で板状に
成形した後、１４００℃で３時間加熱焼成することによ
り、１辺が約５０ｍｍ角の正方形で、厚さが０．５ｍｍ
の燃料電池用の４．５モル％スカンジア部分安定化ジル
コニアシート（ｉ）を得た。このシート焼成体の密度
は、理論密度の９６．８％であった。This zirconia powder (a) was used to form a plate at a pressure of 1000 kg / cm 2 by a rubber pressing method, and then it was heated and baked at 1400 ° C. for 3 hours to form a square with one side of about 50 mm square. And the thickness is 0.5mm
A 4.5 mol% scandia partially stabilized zirconia sheet (i) for the fuel cell was obtained. The density of this sheet fired body was 96.8% of the theoretical density.
【００８６】このシートを、実施例１と同様にしてテス
トピースを作成し、導電率と３点曲げ強度の耐久安定性
を求めた。結果を表２に示す。A test piece was prepared from this sheet in the same manner as in Example 1 to determine the conductivity and durability stability of three-point bending strength. The results are shown in Table 2.
【００８７】比較例２
４．５モル％スカンジア部分安定化ジルコニア粉末（第
一稀元素化学社製：商品名「４．５ＳｃＳＺ」）１００
質量部に対し、イソプロピルアルコール６０質量部と、
チタニウムイソプロポキシドを酸化チタン換算で８．０
質量％となるように添加した混合物を加え、ロータリー
エバーポレータでイソプロパノールを減圧留去した後、
更に減圧乾燥してから８００℃で仮焼し、酸化チタンが
８．０質量％分散した燃料電池用の４．５モル％スカン
ジア部分安定化ジルコニア粉末（ｂ）を得た。この粉末
中のシリカ含量は０．００４質量％、酸化ナトリウム含
量は０．００１質量％であった。Comparative Example 2 4.5 mol% scandia partially stabilized zirconia powder (manufactured by Daiichi Rare Element Chemical Co., Ltd .: trade name "4.5ScSZ") 100
60 parts by mass of isopropyl alcohol with respect to parts by mass,
Titanium isopropoxide converted to titanium oxide 8.0
After adding a mixture added so as to be a mass%, after distilling off the isopropanol under reduced pressure with a rotary evaporator,
Further, it was dried under reduced pressure and then calcined at 800 ° C. to obtain 4.5 mol% scandia partially stabilized zirconia powder (b) for a fuel cell in which 8.0% by mass of titanium oxide was dispersed. The silica content in this powder was 0.004% by mass, and the sodium oxide content was 0.001% by mass.
【００８８】このジルコニア粉末（ｂ）１００質量部に
対し、水７０質量部と、エチルアクリレートを主成分と
する水溶性アクリレート共重合体からなるバインダー
（日本触媒社製：商品名「ＡＴ−５０２」）を固形分換
算で５質量％加え、ボールミルで２０時間分散混合した
後、得られたスラリーをスプレードライ法によって噴霧
乾燥することにより、バインダー添加８．０質量％酸化
チタン分散４．５モル％スカンジア部分安定化ジルコニ
ア粉末（ｃ）を得た。With respect to 100 parts by mass of this zirconia powder (b), 70 parts by mass of water and a binder composed of a water-soluble acrylate copolymer containing ethyl acrylate as a main component (manufactured by Nippon Shokubai Co., Ltd .: trade name "AT-502"). 5% by mass in terms of solid content is added and dispersed and mixed in a ball mill for 20 hours, and then the resulting slurry is spray-dried by a spray drying method to add 8.0% by mass of a binder and 4.5 mol% of titanium oxide dispersion. Scandia partially stabilized zirconia powder (c) was obtained.
【００８９】得られたジルコニア粉末（ｃ）を使用し、
ラバープレス法により１０００ｋｇ／ｃｍ2の圧力で板
状に成形した後、１４００℃で３時間加熱焼成すること
により、１辺が約５０ｍｍ角の正方形で、厚さが０．５
ｍｍの酸化チタン８．０質量％を含む燃料電池用の４．
５モル％スカンジア部分安定化ジルコニアシート（ii）
を得た。このシート焼成体の密度は、理論密度の９５．
０％であった。Using the zirconia powder (c) obtained,
A rubber-press method was used to form a plate at a pressure of 1000 kg / cm 2 , and then the plate was heated and baked at 1400 ° C. for 3 hours to form a square with sides of about 50 mm and a thickness of 0.5.
3. for a fuel cell containing 8.0% by weight of titanium oxide.
5 mol% scandia partially stabilized zirconia sheet (ii)
Got The density of this sheet fired body was 95.
It was 0%.
【００９０】このシートを、実施例１と同様にしてテス
トピースを作成し、導電率と３点曲げ強度の耐久安定性
を求めた。結果を表２に示す。A test piece was prepared from this sheet in the same manner as in Example 1 to determine the conductivity and durability stability of three-point bending strength. The results are shown in Table 2.
【００９１】[0091]
【表１】 [Table 1]
【００９２】[0092]
【表２】 [Table 2]
【００９３】[0093]
【発明の効果】本発明は以上の様に構成されており、ス
カンジア安定化ジルコニア電解質に特定の酸化物を少量
含有させることによって、この種のジルコニア系セラミ
ックスに欠けていたイオン導電性の長期安定性を改善す
ると共に、強度持続性にも優れた燃料電池用のスカンジ
ア安定化ジルコニア電解質を提供し得ることになった。The present invention is constituted as described above, and by including a small amount of a specific oxide in the scandia-stabilized zirconia electrolyte, long-term stability of ionic conductivity lacking in this type of zirconia-based ceramics is obtained. It has become possible to provide a scandia-stabilized zirconia electrolyte for fuel cells, which has improved durability and excellent strength durability.
【００９４】そして、この燃料電池用スカンジア安定化
ジルコニア電解質は、その優れたイオン導電性とその安
定性、および強度持続性を活かし、燃料電池用の酸化物
形固体電解質膜として有効に活用できる。The scandia-stabilized zirconia electrolyte for fuel cells can be effectively used as an oxide-type solid electrolyte membrane for fuel cells by taking advantage of its excellent ionic conductivity, its stability, and durability of strength.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 相川 規一 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 (72)発明者 水谷 安伸 愛知県東海市新宝町507−２ 東邦瓦斯株 式会社内 (72)発明者 鵜飼 健司 愛知県東海市新宝町507−２ 東邦瓦斯株 式会社内 Ｆターム(参考） 4G048 AA03 AB02 AB05 AC06 AE05 5G301 CA30 CD01 5H026 AA06 BB08 EE12 EE13 HH05 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Noriichi Aikawa Hyogo prefecture Himeji city 1 Within Nippon Shokubai Co., Ltd. (72) Inventor Yasunobu Mizutani Toho Gas Co., Ltd. 507-2 Shintakaracho, Tokai City, Aichi Prefecture Inside the company (72) Inventor Kenji Ukai Toho Gas Co., Ltd. 507-2 Shintakaracho, Tokai City, Aichi Prefecture Inside the company F term (reference) 4G048 AA03 AB02 AB05 AC06 AE05 5G301 CA30 CD01 5H026 AA06 BB08 EE12 EE13 HH05
Claims (3)
更に４Ａ族、５Ａ族、７Ａ族および４Ｂ族元素の酸化物
よりなる群から選択される少なくとも１種を、スカンジ
ア安定化ジルコニアに対し０．０１〜５質量％含有する
ことを特徴とする固体酸化物型燃料電池用スカンジア安
定化ジルコニア電解質。1. In scandia-stabilized zirconia,
Further, at least one kind selected from the group consisting of oxides of 4A group, 5A group, 7A group and 4B group elements is contained in an amount of 0.01 to 5 mass% with respect to scandia-stabilized zirconia. Scandia-stabilized zirconia electrolyte for solid fuel cells.
〜１５モル％のスカンジアで安定化されると共に、前記
酸化物として、ＴｉＯ2、Ｎｂ2Ｏ5、Ｔａ2Ｏ 5およびＭ
ｎＯ2よりなる群から選択される酸化物の少なくとも１
種を含有するものである請求項１に記載のスカンジア安
定化ジルコニア電解質。2. The scandia-stabilized zirconia is 3
Stabilized with ~ 15 mol% scandia,
TiO as an oxide2, Nb2OFive, Ta2O FiveAnd M
nO2At least one of the oxides selected from the group consisting of
The scandia ammonium according to claim 1, which contains a seed.
Stabilized zirconia electrolyte.
の酸化物の含有量が、それぞれ０．１質量％以下である
請求項１または２に記載のスカンジア安定化ジルコニア
電解質。3. The scandia-stabilized zirconia electrolyte according to claim 1, wherein the content of silicon oxide and / or oxide of alkali metal is 0.1% by mass or less, respectively.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006087959A1 (en) * | 2005-02-17 | 2006-08-24 | Nippon Shokubai Co., Ltd. | Elctrolyte sheet for solid oxide fuel battery, process for producing the same, and solid oxide fuel battery cell |
| JP2007022870A (en) * | 2005-07-19 | 2007-02-01 | Nippon Shokubai Co Ltd | Mixture for manufacturing ceramic green molding |
| JP2012512521A (en) * | 2008-12-17 | 2012-05-31 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Co-doped YSZ electrolyte for solid oxide fuel cell stack |
| JP2015030641A (en) * | 2013-08-02 | 2015-02-16 | 株式会社日本自動車部品総合研究所 | Gas sensor element, and gas sensor |
| JP2017162607A (en) * | 2016-03-08 | 2017-09-14 | 株式会社日本触媒 | Electrolyte for solid oxide fuel cell |
| EP2492257B1 (en) * | 2009-10-23 | 2018-03-14 | Nippon Shokubai Co., Ltd. | Scandia-stabilised zirconia sintered powder, process for production of scandia-stabilized zirconia sintered powder, process for production of scandia-stabilized zirconia sheet |
| WO2021025051A1 (en) * | 2019-08-06 | 2021-02-11 | 株式会社村田製作所 | Electrolyte sheet for solid oxide fuel battery, production method of electrolyte sheet for solid oxide fuel battery, and single cell for solid oxide fuel battery |
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| JPH06150943A (en) * | 1992-11-05 | 1994-05-31 | Nippon Telegr & Teleph Corp <Ntt> | Oxygen ion conductive material and solid fuel cell |
| JPH07149522A (en) * | 1993-11-30 | 1995-06-13 | Central Res Inst Of Electric Power Ind | Zirconia electrolyte powder and its production |
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2001
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06150943A (en) * | 1992-11-05 | 1994-05-31 | Nippon Telegr & Teleph Corp <Ntt> | Oxygen ion conductive material and solid fuel cell |
| JPH07149522A (en) * | 1993-11-30 | 1995-06-13 | Central Res Inst Of Electric Power Ind | Zirconia electrolyte powder and its production |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006087959A1 (en) * | 2005-02-17 | 2006-08-24 | Nippon Shokubai Co., Ltd. | Elctrolyte sheet for solid oxide fuel battery, process for producing the same, and solid oxide fuel battery cell |
| JP2006228565A (en) * | 2005-02-17 | 2006-08-31 | Nippon Shokubai Co Ltd | ELECTROLYTE SHEET FOR SOLID OXIDE FUEL CELL, PROCESS FOR PRODUCING THE SAME, AND SOLID OXIDE FUEL CELL |
| JP2007022870A (en) * | 2005-07-19 | 2007-02-01 | Nippon Shokubai Co Ltd | Mixture for manufacturing ceramic green molding |
| JP2012512521A (en) * | 2008-12-17 | 2012-05-31 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Co-doped YSZ electrolyte for solid oxide fuel cell stack |
| EP2492257B1 (en) * | 2009-10-23 | 2018-03-14 | Nippon Shokubai Co., Ltd. | Scandia-stabilised zirconia sintered powder, process for production of scandia-stabilized zirconia sintered powder, process for production of scandia-stabilized zirconia sheet |
| JP2015030641A (en) * | 2013-08-02 | 2015-02-16 | 株式会社日本自動車部品総合研究所 | Gas sensor element, and gas sensor |
| JP2017162607A (en) * | 2016-03-08 | 2017-09-14 | 株式会社日本触媒 | Electrolyte for solid oxide fuel cell |
| WO2021025051A1 (en) * | 2019-08-06 | 2021-02-11 | 株式会社村田製作所 | Electrolyte sheet for solid oxide fuel battery, production method of electrolyte sheet for solid oxide fuel battery, and single cell for solid oxide fuel battery |
| JPWO2021025051A1 (en) * | 2019-08-06 | 2021-02-11 | ||
| JP7168090B2 (en) | 2019-08-06 | 2022-11-09 | 株式会社村田製作所 | Electrolyte sheet for solid oxide fuel cell, method for producing electrolyte sheet for solid oxide fuel cell, and single cell for solid oxide fuel cell |
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