JPH0831433A - High strength solid electrolyte material - Google Patents
High strength solid electrolyte materialInfo
- Publication number
- JPH0831433A JPH0831433A JP6186371A JP18637194A JPH0831433A JP H0831433 A JPH0831433 A JP H0831433A JP 6186371 A JP6186371 A JP 6186371A JP 18637194 A JP18637194 A JP 18637194A JP H0831433 A JPH0831433 A JP H0831433A
- Authority
- JP
- Japan
- Prior art keywords
- strength
- added
- electrolyte material
- alumina
- scandia
- 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
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000002001 electrolyte material Substances 0.000 claims abstract description 14
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims abstract description 12
- 241000968352 Scandia <hydrozoan> Species 0.000 claims abstract description 7
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000006104 solid solution Substances 0.000 claims description 3
- 238000010248 power generation Methods 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000007423 decrease Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 32
- 238000005452 bending Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910008337 ZrO(NO3)2.2H2O Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Conductive Materials (AREA)
- Fuel Cell (AREA)
Abstract
(57)【要約】
【目的】 導電率が高く発電特性に優れるのみならず、
機械的特性にも優れた高強度固体電解質材料を提供する
こと。
【構成】 ジルコニア材料中にスカンジアを８〜１５モ
ル％固溶して結晶構造を安定化したスカンジア安定化ジ
ルコニア電解質材料を主成分とし、これに高強度複合材
料としてγ−アルミナが０.１〜２０ 重量％混合されて
いる。固体電解質型燃料電池に適用すれば、電解質板の
薄肉化により内部抵抗が低下し高い発電性能が得られ、
しかも機械強度が高いことにより長期間の耐久性の向上
も達成される。
(57) [Summary] [Purpose] Not only has high conductivity and excellent power generation characteristics,
To provide a high-strength solid electrolyte material having excellent mechanical properties. [Structure] Scandia-stabilized zirconia electrolyte material in which scandia is solid-dissolved in zirconia material in an amount of 8 to 15 mol% to stabilize the crystal structure, and γ-alumina is used as a high-strength composite material in an amount of 0.1 to 0.1 20% by weight is mixed. When applied to a solid oxide fuel cell, the internal resistance decreases due to the thinning of the electrolyte plate, and high power generation performance can be obtained.
Moreover, the high mechanical strength also improves the long-term durability.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、固体電解質型燃料電池
（以下、「ＳＯＦＣ」と略称する。）に用いられる固体
電解質材料に関し、さらに詳しくは固体電解質材料のア
ルミナ分散による高強度化を図ったアルミナ分散型高強
度固体電解質材料に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolyte material used in a solid oxide fuel cell (hereinafter abbreviated as "SOFC"). More specifically, the solid electrolyte material is dispersed in alumina to enhance its strength. And an alumina-dispersed high-strength solid electrolyte material.
【０００２】[0002]
【従来の技術】従来この種の燃料電池としては、電解質
の種類によってリン酸型（以下、「ＰＡＦＣ」と略称す
る。）のもの、溶融炭酸塩型（以下、「ＭＣＦＣ」と略
称する。）のもの、および固体電解質型（ＳＯＦＣ）の
ものが知られている。2. Description of the Related Art Conventionally, as a fuel cell of this type, a phosphoric acid type (hereinafter abbreviated as "PAFC") or a molten carbonate type (hereinafter abbreviated as "MCFC") is used depending on the type of electrolyte. And solid electrolyte type (SOFC) types are known.
【０００３】この中でＳＯＦＣ型燃料電池は、電解質材
料としてリン酸水溶液や溶融炭酸塩のような液体状材料
の代わりにイオン導電性を有する固体電解質材料を用い
たものであり、ＰＡＦＣ型やＭＣＦＣ型の燃料電池に比
べて発電効率が高く、高温度の排熱が得られることか
ら、オンサイト用コージェネレーションシステムへの適
用が期待されている。Among these, the SOFC type fuel cell uses a solid electrolyte material having ionic conductivity instead of a liquid material such as an aqueous phosphoric acid solution or a molten carbonate as an electrolyte material, and is a PAFC type or MCFC. Since it has higher power generation efficiency and higher-temperature exhaust heat than conventional type fuel cells, it is expected to be applied to an on-site cogeneration system.
【０００４】ところでこのＳＯＦＣ型燃料電池の固体電
解質材料としては従来、イットリア安定化ジルコニア材
料（以下、「ＹＳＺ材料」と略称する。）が用いられて
きたが、最近ではこのＹＳＺ材料よりも高い導電率をも
つ材料として、スカンジア安定化ジルコニア材料（以
下、「ＳｃＳＺ材料」と略称する。）が本願出願人によ
る学会発表等により注目を浴びている。このＳｃＳＺ材
料は、ジルコニア材料にスカンジアを固溶させて結晶構
造を安定化させたものである。By the way, a yttria-stabilized zirconia material (hereinafter abbreviated as "YSZ material") has been conventionally used as the solid electrolyte material of the SOFC type fuel cell, but recently, it has higher conductivity than the YSZ material. As a material having a high ratio, a scandia-stabilized zirconia material (hereinafter, abbreviated as “ScSZ material”) has been attracting attention due to a conference presentation by the applicant of the present application. This ScSZ material is one in which scandia is solid-dissolved in a zirconia material to stabilize the crystal structure.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら一方で、
ＳＯＦＣ型燃料電池はその発電容量の増大化が図られ、
たとえば平板型ＳＯＦＣの場合その電解質板の平板面積
を大きくすることによって発電容量を増大させることが
考えられるが、電解質板の平板面積を大きくするために
はその電解質板の材料強度を高める必要がある。そして
材料強度を高めるために単純に電解質板を厚く（０.２
〜０.３ｍｍ）して、強度的にもたせようとすると、今
度は電解質板が薄い場合よりも内部抵抗が増大し、導電
率の低下により発電特性が損なわれるという問題が生じ
る。[Problems to be Solved by the Invention] However, on the other hand,
The SOFC type fuel cell has an increased power generation capacity,
For example, in the case of a flat plate type SOFC, it is possible to increase the power generation capacity by increasing the flat plate area of the electrolyte plate, but in order to increase the flat plate area of the electrolyte plate, it is necessary to increase the material strength of the electrolyte plate. . And to increase the material strength, simply thicken the electrolyte plate (0.2
.About.0.3 mm) to give strength, this time, the internal resistance increases as compared with the case where the electrolyte plate is thin, and there arises a problem that the power generation characteristics are impaired due to the decrease in conductivity.
【０００６】そのような状況の中で、前述のスカンジア
安定化ジルコニア（ＳｃＳＺ）電解質材料は、従来の電
解質材料（イットリア安定化ジルコニアＹＳＺ）よりも
高い導電率を持ってはいるが、平板型ＳＯＦＣの大面積
化に際しては、ハンドリングや構造強度の問題からＹＳ
Ｚ材料と同様ＳｃＳＺ材料の機械強度は十分ではなく、
これを向上させる必要がある。In such a situation, the scandia-stabilized zirconia (ScSZ) electrolyte material described above has a higher conductivity than the conventional electrolyte material (yttria-stabilized zirconia YSZ), but is a flat plate type SOFC. In order to increase the area of the
The mechanical strength of ScSZ material is not sufficient like Z material,
This needs to be improved.
【０００７】そのため本願出願人は先の出願（特願平５
−１７１２０８号）により、ＳｃＳＺ材料にアルミナ
（一般にはα−Ａｌ2Ｏ3が使用される）を複合化させる
ことによってＳｃＳＺ電解質材料の機械強度を高める技
術内容を提示した。しかしこれには以下の問題点があっ
た。すなわち、 α−Ａｌ2Ｏ3の添加にともない電解質材料の内部抵抗
が著しく増大するため、導電率が低下して発電性能が損
なわれる。 材料強度が低いため、機械的・熱的疲労破損を起こし
やすく、長期間の使用に耐え得ず、耐久性に劣る。Therefore, the applicant of the present application has filed an earlier application (Japanese Patent Application No.
No. 171208), a technical content for increasing the mechanical strength of the ScSZ electrolyte material by compounding alumina (generally α-Al 2 O 3 is used) with the ScSZ material was presented. However, this has the following problems. That is, since the internal resistance of the electrolyte material is remarkably increased with the addition of α-Al 2 O 3 , the conductivity is lowered and the power generation performance is impaired. Due to its low material strength, it is prone to mechanical and thermal fatigue damage, cannot withstand long-term use, and has poor durability.
【０００８】本発明は、このような問題点を解決するた
めになされたものであり、その目的とするところは、高
い導電率を維持しつつγ−アルミナの添加によりα−ア
ルミナによる複合強化よりもさらに機械的特性に優れた
固体電解質材料を提供することにある。これにより、Ｓ
ＯＦＣ型燃料電池としての発電特性はもとより耐久性能
をも向上させ、大容量化への要求に応えんとするもので
ある。The present invention has been made in order to solve such a problem, and its purpose is to improve the composite strengthening by α-alumina by adding γ-alumina while maintaining high conductivity. Another object is to provide a solid electrolyte material having further excellent mechanical properties. This allows S
In addition to improving the power generation characteristics of the OFC fuel cell, the durability performance is also improved to meet the demand for larger capacity.
【０００９】[0009]
【課題を解決するための手段】このような目的を達成す
るため本発明は、ジルコニア材料にスカンジアを固溶さ
せて結晶構造を安定化させたスカンジア安定化ジルコニ
ア電解質材料を主成分とし、これにγ−アルミナを高強
度複合材料として分散させてなることを要旨とするもの
である。この場合にスカンジアはジルコニア材料中に８
〜１５モル％固溶されているのが望ましく、これにより
固体電解質材料であるジルコニア材料の結晶構造の安定
化が図られる。In order to achieve such an object, the present invention is based on a scandia-stabilized zirconia electrolyte material in which scandia is solid-dissolved in a zirconia material to stabilize the crystal structure. The gist is that γ-alumina is dispersed as a high-strength composite material. In this case scandia is 8 in the zirconia material.
It is desirable that the solid solution is ˜15 mol%, which stabilizes the crystal structure of the zirconia material that is the solid electrolyte material.
【００１０】またこのスカンジア安定化ジルコニア電解
質材料にγ−アルミナを０.１ 〜２０ｗｔ％の範囲で適
量配合することにより曲げ強度等の機械的特性が向上す
る。これによりα−Ａｌ2Ｏ3を添加したコンポジット材
料の約１.５倍 、材料強化されていないＳｃＳＺ材料の
約３倍の強度を図ることができる。Mechanical properties such as bending strength are improved by adding an appropriate amount of γ-alumina to the scandia-stabilized zirconia electrolyte material in the range of 0.1 to 20 wt%. As a result, the strength of the composite material to which α-Al 2 O 3 is added can be increased about 1.5 times, and the strength of the ScSZ material without material reinforcement can be increased about 3 times.
【００１１】[0011]
【実施例】以下に本発明について各種実験を行なったの
でその結果を詳細に説明する。 （実験方法）初めに図１に本発明のＳＯＦＣ型燃料電池
に供されるスカンジア安定化ジルコニア電解質の調製法
について示し、これについて説明する。EXAMPLES Various experiments were carried out on the present invention, and the results will be described in detail below. (Experimental Method) First, FIG. 1 shows a method for preparing a scandia-stabilized zirconia electrolyte to be used in the SOFC type fuel cell of the present invention, which will be described.
【００１２】１．ＳｃＳＺ原料粉末の調整 ＳｃＳＺ原料粉末は、Ｓｃ2Ｏ3を原子レベルで均一に混
合することを目的として、ゾルゲル法（蟻酸法）、あ
るいは含浸法により調製した。はじめに、ゾルゲル
法について説明すると、所定量のＳｃ2Ｏ3（９９.９％
）を加熱した濃硝酸に溶解させ、蒸留水で希釈したの
ち、所定量のＺｒＯ（ＮＯ3 ）2・２Ｈ2Ｏを加えた。こ
の溶液に蟻酸とポリエチレングリコールを加え、攪拌し
ながら加熱固化して前駆体を得た。そして、得られた前
駆体を８００℃で１２時間仮焼して結晶化させ、ＳｃＳ
Ｚ原料粉末とした。この段階で大部分のＳｃ2Ｏ3はＺｒ
Ｏ2に固溶している。1. Preparation of ScSZ Raw Material Powder The ScSZ raw material powder was prepared by a sol-gel method (formic acid method) or an impregnation method for the purpose of uniformly mixing Sc 2 O 3 at the atomic level. First, the sol-gel method will be explained. A predetermined amount of Sc 2 O 3 (99.9%
) Was dissolved in heated concentrated nitric acid and diluted with distilled water, and then a predetermined amount of ZrO (NO 3 ) 2 .2H 2 O was added. Formic acid and polyethylene glycol were added to this solution, and the mixture was heated and solidified with stirring to obtain a precursor. Then, the obtained precursor is calcined at 800 ° C. for 12 hours to be crystallized, and ScS
Z raw material powder was used. At this stage, most of Sc 2 O 3 is Zr
It forms a solid solution in O 2 .
【００１３】次に含浸法について説明すると、所定量
のＳｃ2Ｏ3（９９.９％） を加熱した濃硝酸に溶解さ
せ、やはり蒸留水で希釈したのち、所定量のＺｒＯ2
（東ソー社製品ジルコニア「ＴＺ−Ｏ」）に加え、ジル
コニアに含浸させる。次にこの溶液を加熱固化してＳｃ
ＳＺ原料粉末とした。Explaining the impregnation method, a predetermined amount of Sc 2 O 3 (99.9%) is dissolved in heated concentrated nitric acid, diluted with distilled water, and then a predetermined amount of ZrO 2 is added.
(Zirconia "TZ-O" manufactured by Tosoh Corporation), and zirconia is impregnated. Next, this solution is heated and solidified to obtain Sc.
SZ raw material powder was used.
【００１４】２．ＳｃＳＺ−Ａｌ2Ｏ3複合材料の調整 アルミナの種類のちがいにより、ＳｃＳＺ−Ａｌ2Ｏ3複
合材料の調整方法を変えた。 α−Ａｌ2Ｏ3（あるいは、γ−Ａｌ2Ｏ3）を添加した
複合材料の調整。 所定量のα−Ａｌ2Ｏ3（あるいは、γ−Ａｌ2Ｏ3）をＳ
ｃＳＺ原料粉末に加えたのち、ボールミル機で湿式混合
した。湿式混合の溶液には、エチルアルコールを用い
た。次に、この混合液を加熱乾燥して、ＳｃＳＺ−Ａｌ
2Ｏ3複合材料とした。 Ａｌ（Ｏ−ｉｐｒ）3を添加した複合材料の調整 所定量のアルミニウムイソプロポキシド（Ａｌ（Ｏ−ｉ
ｐｒ）3） を濃硝酸に溶解させ、蒸留水で希釈した後、
ＳｃＳＺ原料粉末に加えた。次に、この混合液を攪拌し
ながら加熱乾燥し、ＳｃＳＺ−Ａｌ2Ｏ3複合材料とし
た。2. The difference in the type of adjustment alumina ScSZ-Al 2 O 3 composite material, changing the method of adjusting the ScSZ-Al 2 O 3 composite material. Preparation of a composite material to which α-Al 2 O 3 (or γ-Al 2 O 3 ) is added. A predetermined amount of α-Al 2 O 3 (or γ-Al 2 O 3 ) is added to S.
After being added to the cSZ raw material powder, it was wet mixed with a ball mill. Ethyl alcohol was used as the solution for wet mixing. Next, this mixed liquid is dried by heating to give ScSZ-Al.
2 O 3 composite material was used. Preparation of Composite Material Added with Al (O-ipr) 3 A predetermined amount of aluminum isopropoxide (Al (O-i-
pr) 3 ) is dissolved in concentrated nitric acid and diluted with distilled water,
ScSZ raw material powder was added. Next, this mixed solution was heated and dried with stirring to obtain a ScSZ-Al 2 O 3 composite material.
【００１５】３．焼結体（試験片）の作製 上記１、２で得られた原料粉末を金型で一軸成形した
後、静水圧プレス（ＣＩＰ）２０００ｋｇ／ｃｍ2 によ
り成形した。この成形体を１５００〜１７００℃で、５
〜１５時間焼成し、試験片を得た。3. Preparation of Sintered Body (Test Piece) The raw material powders obtained in the above 1 and 2 were uniaxially molded by a mold and then molded by a hydrostatic pressure press (CIP) of 2000 kg / cm 2 . This molded body is heated at 1500 to 1700 ° C. for 5
The test piece was obtained by firing for ~ 15 hours.
【００１６】４．特性評価 導電率 導電率の測定は、直径７ｍｍ，長さ２〜３ｍｍの円板状
焼結体の両面に白金電極を焼き付け、交流インピーダン
ス法により行った。周波数は１〜１００ｋＨｚの範囲
で、Ｃｏｌｅ−Ｃｏｌｅ Ｐｌｏｔで得られた抵抗値と
試験片の寸法から試料の導電率を求めた。 曲げ強度 試験片の曲げ強度は、ＪＩＳ Ｒ１６０１−１９８１
「ファインセラミックスの曲げ強さ試験方法」に準じ、
３点曲げ試験により行った。試験片の形状は、３ｍｍ
（Ｂ）×４ｍｍ（Ｗ）×４０ｍｍ（Ｌ）の長方形の角柱
とした。4. Characteristic Evaluation Conductivity The conductivity was measured by an AC impedance method by baking platinum electrodes on both sides of a disk-shaped sintered body having a diameter of 7 mm and a length of 2 to 3 mm. The frequency was in the range of 1 to 100 kHz, and the conductivity of the sample was obtained from the resistance value obtained by Cole-Cole Plot and the size of the test piece. Bending strength The bending strength of the test piece is JIS R1601-1981.
According to the "testing method for bending strength of fine ceramics",
It was conducted by a three-point bending test. The shape of the test piece is 3 mm
(B) x 4 mm (W) x 40 mm (L) rectangular prism.
【００１７】（実験結果） 導電率 図２にアルミナ添加による導電率の変化特性のデータを
示す。用いられた固体電解質材料は１１モル％ＳｃＳＺ
材料であり、導電率の測定温度は通常のＳＯＦＣ型燃料
電池の運転温度である１０００℃とした。横軸にアルミ
ナ添加量（ｗｔ％）を採り、縦軸に導電率（Ｓ／ｃｍ）
を示す。アルミナ添加量は、０〜２０ｗｔ％とした。(Experimental Results) Conductivity FIG. 2 shows data on the change characteristic of conductivity due to addition of alumina. The solid electrolyte material used was 11 mol% ScSZ.
It was a material, and the measurement temperature of conductivity was 1000 ° C. which is the operating temperature of a normal SOFC fuel cell. Alumina addition amount (wt%) is taken on the horizontal axis, and conductivity (S / cm) is taken on the vertical axis.
Indicates. The amount of alumina added was 0 to 20 wt%.
【００１８】この結果α−Ａｌ2Ｏ3を添加したもの、Ａ
ｌ（Ｏ−ｉｐｒ）3 を添加したもの、およびγ−Ａｌ2
Ｏ3を添加したもののいずれもアルミナ添加量を増すに
つれて導電率が低下する傾向が見られたが、その中でα
−Ａｌ2Ｏ3を添加したものが最も導電率の低下が著し
く、次いでＡｌ（Ｏ−ｉｐｒ）3 を添加したもの、最も
導電率の低下が少ないのがγ−Ａｌ2Ｏ3を添加したもの
であった。As a result, the product to which α-Al 2 O 3 was added, A
1 (O-ipr) 3 added, and γ-Al 2
It was found that the conductivity of each of the materials added with O 3 tended to decrease as the amount of alumina added increased.
-Al 2 O 3 has the most significant decrease in conductivity, then Al (O-ipr) 3 has been added, and the one with the least decrease in conductivity has γ-Al 2 O 3 added Met.
【００１９】さらにそのデータの内容を解析すると、α
−Ａｌ2Ｏ3を添加したものは、アルミナ添加量が１ｗｔ
％程度の少ない段階ですでに導電率の低下度合いが大き
く、アルミナ添加量およそ５ｗｔ％程度で導電率が０.
２Ｓ／ｃｍ 以下にまで落ち、十分な発電性能が得られ
ない状態となった。これに対してＡｌ（Ｏ−ｉｐｒ）3
を添加したものは、アルミナ添加量がおよそ１０ｗｔ％
で導電率が０.２ Ｓ／ｃｍ以下にまで落ちることがわか
った。Further analyzing the contents of the data, α
-Al 2 O 3 was added, the amount of alumina added was 1 wt.
The degree of decrease in conductivity is already large when the percentage is low, and the conductivity is less than about 5 wt% alumina.
It fell to 2 S / cm or less, and it became a state where sufficient power generation performance was not obtained. On the other hand, Al (O-ipr) 3
The amount of alumina added is about 10 wt%
It was found that the electrical conductivity dropped to 0.2 S / cm or less.
【００２０】そしてγ−Ａｌ2Ｏ3を添加したものは、ア
ルミナ添加量が１ｗｔ％程度の少ない段階では導電率
０.２８Ｓ／ｃｍ 以上の値を示し、またアルミナ添加量
が１０ｗｔ％程度まで増量しても導電率は０.２５Ｓ／
ｃｍ 程度の高い値を維持するものであり、実機運転で
も高い発電性能が得られるものである。When γ-Al 2 O 3 is added, the conductivity shows a value of 0.28 S / cm or more when the amount of alumina added is as low as about 1 wt%, and the amount of alumina added is increased to about 10 wt%. Even if the conductivity is 0.25S /
It maintains a high value of about cm 3, and can obtain high power generation performance even in actual operation.
【００２１】曲げ強度 図３にアルミナ添加による曲げ強度の変化特性のデータ
を示す。固体電解質材料は前述の導電率測定に供した材
料と同じもの、すなわち１１モル％ＳｃＳＺ材料であ
る。横軸にアルミナ添加量（ｗｔ％）を採り、縦軸に曲
げ強度（ＭＰａ）を示す。Bending Strength FIG. 3 shows data on the change characteristics of bending strength due to the addition of alumina. The solid electrolyte material is the same as the material used for the conductivity measurement, that is, the 11 mol% ScSZ material. The horizontal axis shows the amount of alumina added (wt%), and the vertical axis shows the bending strength (MPa).
【００２２】この結果、α−Ａｌ2Ｏ3を添加したもの、
Ａｌ（Ｏ−ｉｐｒ）3 を添加したもの、およびγ−Ａｌ
2Ｏ3を添加したもののいずれの場合もアルミナ添加量の
増加とともに曲げ強度が増大することがわかった。その
中で特にγ−Ａｌ2Ｏ3を添加したものの曲げ強度の増加
度が最も大きく、次いでＡｌ（Ｏ−ｉｐｒ）3 を添加し
たものであり、最も曲げ強度の増加度の小さかったのが
α−Ａｌ2Ｏ3を添加したものであった。As a result, the one to which α-Al 2 O 3 was added,
Al (O-ipr) 3 added, and γ-Al
It was found that the flexural strength increased as the amount of alumina added increased in any case where 2 O 3 was added. Among them, in particular, the one in which γ-Al 2 O 3 was added showed the largest increase in bending strength, and the one in which Al (O-ipr) 3 was added next, with the smallest increase in bending strength being α. were those added -Al 2 O 3.
【００２３】さらにそれらのデータの内容をよく解析す
ると、いずれの添加物 （α−Ａｌ2Ｏ3，Ａｌ（Ｏ−ｉ
ｐｒ）3，γ−Ａｌ2Ｏ3）の場合もアルミナ添加量が１
ｗｔ％程度で急激に曲げ強度が増大し、その中でγ−Ａ
ｌ2Ｏ3を添加したものが最も高い曲げ強度値を示すこと
が明らかとなった。そしてまたアルミナ添加量が増すに
つれていずれの添加物の場合も曲げ強度が徐々に増加し
ていくが、その中でγ−Ａｌ2Ｏ3を添加したものは常に
最も高い曲げ強度値を示すものであった。Further, when the contents of these data are well analyzed, it can be seen that any of the additives (α-Al 2 O 3 , Al (O-i
In the case of pr) 3 and γ-Al 2 O 3 ), the amount of alumina added is 1
The bending strength rapidly increases at about wt%, and γ-A
It was revealed that the one to which l 2 O 3 was added exhibited the highest bending strength value. Also, as the amount of alumina added increases, the flexural strength gradually increases in the case of any of the additives, of which the one to which γ-Al 2 O 3 is added always shows the highest flexural strength value. there were.
【００２４】ちなみに本発明にかかるＳｃＳＺ材料にγ
−Ａｌ2Ｏ3を添加したものは、従来のα−Ａｌ2Ｏ3を添
加したコンポジット材料の約１.５倍 、Ａｌ2Ｏ3による
材料強化がなされていないＳｃＳＺ材料の約３倍の強度
を持つことが明らかになった。したがって本発明のよう
にＳｃＳＺ電解質材料をγ−Ａｌ2Ｏ3により複合強化し
たものでは、ＳＯＦＣ電解質板の厚さを、α−Ａｌ2Ｏ3
を添加したコンポジット材料の約２／３（０.２ｍｍ程
度） 、材料強化されていないＳｃＳＺ材料の約１／３
（０.１ｍｍ程度）にすることができる。Incidentally, the ScSZ material according to the present invention has γ
-Al 2 O 3 was added, the strength was about 1.5 times that of the conventional composite material to which α-Al 2 O 3 was added, and about 3 times the strength of the ScSZ material that was not reinforced by Al 2 O 3. It became clear to have. Therefore, in the case where the ScSZ electrolyte material is compositely reinforced with γ-Al 2 O 3 as in the present invention, the thickness of the SOFC electrolyte plate is set to α-Al 2 O 3
Approximately 2/3 (about 0.2 mm) of the composite material with the addition of approx. 1/3 of the non-reinforced ScSZ material
(About 0.1 mm).
【００２５】そして図２および図３のデータから言える
ことは、スカンジア安定化ジルコニア（ＳｃＳＺ）材料
にγ−Ａｌ2Ｏ3を添加することによって高い導電率を維
持しつつ、曲げ強度特性も良好な状態が得られるという
ことである。そして特にγ−Ａｌ2Ｏ3の添加量としては
１ｗｔ％程度ですでに高い曲げ強度値が得られる（図３
より）ものであるから、あえてそれ以上にアルミナ添加
量を増す必要はないと思われる。しかし、実機運転にお
いてより高い機械的特性を要求するならば、アルミナの
添加量として１ｗｔ％以上〜２０ｗｔ％程度まではそれ
程導電率を低下させることなく使用できるものである。The data shown in FIGS. 2 and 3 can be said to be that by adding γ-Al 2 O 3 to the scandia-stabilized zirconia (ScSZ) material, the high electrical conductivity is maintained and the bending strength characteristics are also excellent. It means that the state can be obtained. Particularly, when the amount of γ-Al 2 O 3 added is about 1 wt%, a high bending strength value is already obtained (FIG. 3).
Therefore, it is not necessary to increase the amount of alumina added more than that. However, if higher mechanical properties are required in the actual machine operation, the amount of alumina added can be used up to about 1 wt% to 20 wt% without reducing the conductivity so much.
【００２６】以上の結果をまとめると、ＳＯＦＣに本発
明による電解質材料を用いることで以下の効果が期待で
きる。 電解質板をさらに薄くし、内部抵抗を減らすことで、
高い発電性能が得られる。 電解質板の強度が確保でき、ＳＯＦＣの信頼性が向上
する。 材料強度が高いため、機械的・熱的疲労破壊を起こし
にくく、長期間の使用に耐え得るものである。Summarizing the above results, the following effects can be expected by using the electrolyte material according to the present invention for SOFC. By making the electrolyte plate thinner and reducing the internal resistance,
High power generation performance can be obtained. The strength of the electrolyte plate can be secured, and the reliability of SOFC is improved. Since the material strength is high, mechanical / thermal fatigue fracture is unlikely to occur and it can withstand long-term use.
【００２７】尚、本発明は上記実施例に何ら限定される
ものではなく、本発明の趣旨を逸脱しない範囲で種々の
態様が考えられる。たとえば、ＳｃＳＺ原料粉末の調整
は上記実施例ではゾルゲル法や含浸法によるものを紹介
したが、これらの方法による粉末原料の調整が最も均一
な混合粉末を得ることができて固体電解質材料としての
機械強度の特性に好結果が得られるからである。これ以
外にも従来一般に行なわれているように、ジルコニア粉
末原料とスカンジア粉末原料とをボールミル等により機
械的に混合する方法によるものであっても構わない。Ｙ
ＳＺにγ−Ａｌ2Ｏ3を添加したものも同様の効果が期待
できる。The present invention is not limited to the above embodiments, and various modes can be considered without departing from the gist of the present invention. For example, the preparation of the ScSZ raw material powder was introduced by the sol-gel method or the impregnation method in the above-mentioned embodiment. However, the preparation of the powder raw material by these methods can obtain the most uniform mixed powder and can be used as a solid electrolyte material. This is because good results can be obtained in the strength characteristics. In addition to this, a method of mechanically mixing the zirconia powder raw material and the scandia powder raw material by a ball mill or the like may be used, which is generally performed conventionally. Y
A similar effect can be expected in the case where γ-Al 2 O 3 is added to SZ.
【００２８】[0028]
【発明の効果】以上説明したことから明かなように、本
発明に係るγ−Ａｌ2Ｏ3複合分散したスカンジア安定化
ジルコニア（ＳｃＳＺ）電解質材料によれば、従来のイ
ットリウム安定化ジルコニア（ＹＳＺ）材料に較べて導
電率が高く発電特性に優れるのみならず、α−Ａｌ2Ｏ3
に代えてγ−Ａｌ2Ｏ3材料により複合高強度化を図った
ものであるから、固体電解質材料としての強度を維持で
きるものである。したがってその材料強度が高い分電解
質板の薄肉化による内部抵抗の減少を図れ、より高い発
電性能が得られ、また材料強度が高いことによる機械的
・熱的疲労破壊も少なく、長期間の使用にも耐え得るも
のであり、オンサイト用コージェネレーションシステム
への実用化へ大いに寄与し得るものである。As is apparent from the above description, according to the scandia-stabilized zirconia (ScSZ) electrolyte material according to the present invention in which γ-Al 2 O 3 is dispersed, conventional yttrium-stabilized zirconia (YSZ) is used. Not only does it have high electrical conductivity and excellent power generation characteristics compared to materials, but also α-Al 2 O 3
In place of the above, since the composite high strength is achieved by using the γ-Al 2 O 3 material, the strength as a solid electrolyte material can be maintained. Therefore, since the material strength is high, the internal resistance can be reduced due to the thinning of the electrolyte plate, higher power generation performance can be obtained, and mechanical / thermal fatigue breakdown due to the high material strength is also less, making it suitable for long-term use. Can withstand, and can greatly contribute to the practical application to an on-site cogeneration system.
【図１】本発明に係る固体電解質材料の調製法を説明す
るための工程図である。FIG. 1 is a process chart for explaining a method for preparing a solid electrolyte material according to the present invention.
【図２】本発明に係る固体電解質材料の発電特性を説明
するためアルミナ添加量と導電率との関係を示した図で
ある。FIG. 2 is a diagram showing the relationship between the amount of alumina added and the electrical conductivity for explaining the power generation characteristics of the solid electrolyte material according to the present invention.
【図３】本発明に係る固体電解質材料の機械的特性を説
明するためアルミナ添加量と曲げ強度との関係を示した
図である。FIG. 3 is a diagram showing the relationship between the amount of alumina added and the bending strength for explaining the mechanical properties of the solid electrolyte material according to the present invention.
Claims (2)
て結晶構造を安定化させたスカンジア安定化ジルコニア
電解質材料を主成分とし、これにγ−アルミナを高強度
複合材料として分散させてなることを特徴とする高強度
固体電解質材料。1. A scandia-stabilized zirconia electrolyte material in which scandia is solid-dissolved in a zirconia material to stabilize the crystal structure, and γ-alumina is dispersed as a high-strength composite material in the main component. High strength solid electrolyte material.
材料にはスカンジアが８〜１５モル％固溶され、前記γ
−アルミナは前記スカンジア安定化ジルコニア電解質材
料中に０.１ 〜２０重量％混合されてなることを特徴と
する請求項１に記載の高強度固体電解質材料。2. The scandia-stabilized zirconia electrolyte material contains 8 to 15 mol% of scandia as a solid solution, and the γ
The high-strength solid electrolyte material according to claim 1, wherein alumina is mixed in the scandia-stabilized zirconia electrolyte material in an amount of 0.1 to 20% by weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18637194A JP3331056B2 (en) | 1994-07-14 | 1994-07-14 | Dispersion strengthened solid electrolyte material and solid electrolyte sintered body using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18637194A JP3331056B2 (en) | 1994-07-14 | 1994-07-14 | Dispersion strengthened solid electrolyte material and solid electrolyte sintered body using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0831433A true JPH0831433A (en) | 1996-02-02 |
| JP3331056B2 JP3331056B2 (en) | 2002-10-07 |
Family
ID=16187219
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18637194A Expired - Lifetime JP3331056B2 (en) | 1994-07-14 | 1994-07-14 | Dispersion strengthened solid electrolyte material and solid electrolyte sintered body using the same |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10214519A (en) * | 1996-12-31 | 1998-08-11 | Praxair Technol Inc | Solid electrolyte membrane having component for improving mechanical and catalytic characteristics |
| JP2000128545A (en) * | 1998-08-26 | 2000-05-09 | Praxair Technol Inc | Production of ceramic film |
| EP1202370A1 (en) * | 2000-10-23 | 2002-05-02 | Toho Gas Co., Ltd. | Solid oxide fuel cell |
| JP2003068324A (en) * | 2001-06-15 | 2003-03-07 | Ngk Spark Plug Co Ltd | Oxygen ion conductive solid electrolyte, electrochemical device and solid electrolyte fuel cell using the same |
| JP2022157597A (en) * | 2021-03-31 | 2022-10-14 | 株式会社ノリタケカンパニーリミテド | Solid electrolyte structure and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107462A (en) * | 1992-08-12 | 1994-04-19 | Nippon Telegr & Teleph Corp <Ntt> | Oxygen ion conductor and solid fuel cell |
-
1994
- 1994-07-14 JP JP18637194A patent/JP3331056B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107462A (en) * | 1992-08-12 | 1994-04-19 | Nippon Telegr & Teleph Corp <Ntt> | Oxygen ion conductor and solid fuel cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10214519A (en) * | 1996-12-31 | 1998-08-11 | Praxair Technol Inc | Solid electrolyte membrane having component for improving mechanical and catalytic characteristics |
| JP2000128545A (en) * | 1998-08-26 | 2000-05-09 | Praxair Technol Inc | Production of ceramic film |
| EP1202370A1 (en) * | 2000-10-23 | 2002-05-02 | Toho Gas Co., Ltd. | Solid oxide fuel cell |
| JP2003068324A (en) * | 2001-06-15 | 2003-03-07 | Ngk Spark Plug Co Ltd | Oxygen ion conductive solid electrolyte, electrochemical device and solid electrolyte fuel cell using the same |
| JP2022157597A (en) * | 2021-03-31 | 2022-10-14 | 株式会社ノリタケカンパニーリミテド | Solid electrolyte structure and use thereof |
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| Publication number | Publication date |
|---|---|
| JP3331056B2 (en) | 2002-10-07 |
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