JPH07262819A - Porous conductive material powder and its manufacture, and porous electrode using this material powder - Google Patents
Porous conductive material powder and its manufacture, and porous electrode using this material powderInfo
- Publication number
- JPH07262819A JPH07262819A JP6048191A JP4819194A JPH07262819A JP H07262819 A JPH07262819 A JP H07262819A JP 6048191 A JP6048191 A JP 6048191A JP 4819194 A JP4819194 A JP 4819194A JP H07262819 A JPH07262819 A JP H07262819A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- conductive material
- material powder
- porous
- powder
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 35
- 239000004020 conductor Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000000463 material Substances 0.000 title 1
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims description 18
- 229920000620 organic polymer Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 26
- 239000007784 solid electrolyte Substances 0.000 abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 abstract description 13
- 239000000758 substrate Substances 0.000 abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002003 electrode paste Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 239000007772 electrode material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010248 power generation Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000003411 electrode reaction Methods 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000004931 aggregating effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- BQENXCOZCUHKRE-UHFFFAOYSA-N [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O Chemical compound [La+3].[La+3].[O-][Mn]([O-])=O.[O-][Mn]([O-])=O.[O-][Mn]([O-])=O BQENXCOZCUHKRE-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Conductive Materials (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、多孔質性の導電性材料
粉末とその製法及びそれを用いた多孔質電極に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous conductive material powder, a method for producing the same, and a porous electrode using the same.
【０００２】[0002]
【従来の技術】例えば、燃料の化学的なエネルギーを電
気化学的な手段によって、直接電気エネルギーに変換す
る燃料電池のうち、１０００℃程度の高温で運転される
固体電解質型燃料電池がある。この燃料電池は、電気を
発生させる発電部に、固体電解質を挟んで互いに対向し
あう燃料極及び空気極があり、これらの電極には多孔質
のセラミック膜が用いられている。そして、このような
多孔質電極の一般的な製造方法として、多孔質性の電極
ペーストを、セラミック基板であるＹＳＺ（イットリア
安定化ジルコニア）のような固体電解質の焼結体に塗布
して焼き付ける方法がある。2. Description of the Related Art For example, among fuel cells that directly convert the chemical energy of fuel into electrical energy by an electrochemical means, there is a solid oxide fuel cell that operates at a high temperature of about 1000.degree. This fuel cell has a fuel electrode and an air electrode, which face each other with a solid electrolyte in between, in a power generation section that generates electricity, and a porous ceramic membrane is used for these electrodes. As a general manufacturing method of such a porous electrode, a method of applying a porous electrode paste to a sintered body of a solid electrolyte such as YSZ (yttria-stabilized zirconia) which is a ceramic substrate and baking it There is.
【０００３】[0003]
【発明が解決しようとする課題】燃料電池の多孔質電極
としては、見掛けの電極面積に占める電極反応面積が大
きいことが必要である。この条件を満たすためには、多
孔質電極内部の電極の表面積を大きくしなければなら
ず、このため一般に、電極材の粒子はより小さく、５μ
ｍ以下であることが必要とされている。The porous electrode of a fuel cell is required to have a large electrode reaction area in the apparent electrode area. To meet this condition, the surface area of the electrode inside the porous electrode must be increased, which generally results in smaller particles of the electrode material, 5 μm.
It is required to be m or less.
【０００４】しかし、多孔質電極を作製する場合、セラ
ミック基板である固体電解質の焼結体に、このような粒
子の小さい電極材のペーストを塗布して焼き付けると、
粒子が小さいために、これが凝集して縮みやすくなる。
縮みが起こると電極と固体電解質の界面に応力が発生す
るため、電極が固体電解質から剥離したり、電極内部に
亀裂が生じるという問題がある。However, when a porous electrode is manufactured, when a paste of an electrode material having such small particles is applied to a sintered body of a solid electrolyte which is a ceramic substrate and baked,
Since the particles are small, they tend to aggregate and shrink.
When the shrinkage occurs, stress is generated at the interface between the electrode and the solid electrolyte, so that there is a problem that the electrode is separated from the solid electrolyte or a crack is generated inside the electrode.
【０００５】一方、焼き付けのときに粒子が縮まないよ
うにするため、粒子の大きな電極材を使うと、見掛けの
電極面積に占める電極反応面積が小さくなり、性能が低
下するという問題がある。On the other hand, if an electrode material having large particles is used in order to prevent the particles from shrinking during baking, there is a problem that the electrode reaction area occupying the apparent electrode area becomes small and the performance deteriorates.
【０００６】また、より高性能な多孔質電極であるため
には、電極内部に適当量の気孔を有することも必要であ
るが、気孔を作るために加える有機高分子の量が増える
に従い、電極の焼き付け時に電極材の粒子が凝集して、
より縮みやすくなる。縮みが起こると電極と固体電解質
の界面で応力が発生するため、この場合も電極が固体電
解質から剥離したり、電極内部に亀裂が生じるという問
題がある。Further, in order to obtain a higher performance porous electrode, it is necessary to have an appropriate amount of pores inside the electrode. However, as the amount of organic polymer added to create pores increases, the electrode Particles of the electrode material aggregate during baking
It will shrink more easily. When the shrinkage occurs, stress is generated at the interface between the electrode and the solid electrolyte, and in this case also, there is a problem that the electrode is separated from the solid electrolyte or a crack is generated inside the electrode.
【０００７】そこで本発明の目的は、粒子の大きな電極
材を用いず、電極材の粒子が小さくとも、焼き付け時に
粒子が凝集せず縮むことがない電極材を提供すること、
また、気孔を作るため、電極材に有機高分子を加えて
も、焼き付け時に粒子が凝集せず縮むことがない電極材
を提供すること、そしてこれにより、電極と固体電解質
の界面に応力が発生することがなく、電極が固体電解質
から剥離したり、電極内部に亀裂が生じることのない、
より高性能な多孔質電極を提供することにある。[0007] Therefore, an object of the present invention is to provide an electrode material which does not shrink even when the particle size of the electrode material is small, without aggregating the particles during baking, without using an electrode material having large particles.
In addition, to create pores, it is possible to provide an electrode material in which particles do not aggregate and shrink during baking even when an organic polymer is added to the electrode material, and this causes stress at the interface between the electrode and the solid electrolyte. Without peeling the electrode from the solid electrolyte or cracking inside the electrode,
The object is to provide a higher performance porous electrode.
【０００８】[0008]
【課題を解決するための手段】本発明は、請求項１にお
いて、多孔質性の導電性材料粉末は、粒子径が５μｍ以
下の粒子が凝集し、かつ、気孔を有することを特徴とす
るものである。According to a first aspect of the present invention, the porous conductive material powder is characterized in that particles having a particle diameter of 5 μm or less are aggregated and have pores. Is.
【０００９】また、請求項２において、多孔質性の導電
性材料粉末の製造方法は、粒子径が５μｍ以下の導電性
材料粉末と有機高分子を混ぜて焼成することを特徴とす
るものである。In the second aspect of the present invention, the method for producing the porous conductive material powder is characterized in that the conductive material powder having a particle diameter of 5 μm or less and the organic polymer are mixed and fired. .
【００１０】また、請求項３において、多孔質電極は、
粒子径が５μｍ以下の粒子が凝集し、かつ、気孔を有す
ることを特徴とするものである。Further, in claim 3, the porous electrode is
It is characterized in that particles having a particle diameter of 5 μm or less are aggregated and have pores.
【００１１】[0011]
【作用】本発明の請求項１によれば、導電性材料粉末
は、粒子径が５μｍ以下の粒子が凝集し、かつ、気孔を
有することにより、多孔質性となる。この多孔質導電性
材料粉末を電極ペーストに調製する際には、すでに多孔
質性を備えているところから、気孔を作るために加える
有機高分子は少量でよい。例えば、これを固体電解質基
板に塗布して焼き付けると、導電性材料粉末はすでにか
なり凝集しており、加えた有機高分子も少量であるた
め、凝集による縮み量は従来より低く抑えることができ
る。このため、電極と固体電解質の界面に応力が発生し
にくく、電極の剥離や亀裂がほとんど起こらなくなる。According to the first aspect of the present invention, the conductive material powder becomes porous by aggregating particles having a particle diameter of 5 μm or less and having pores. When preparing this porous conductive material powder into an electrode paste, a small amount of organic polymer may be added to form pores because it is already porous. For example, when this is applied to a solid electrolyte substrate and baked, the conductive material powder is already agglomerated and the added organic polymer is also a small amount, so the amount of shrinkage due to agglomeration can be suppressed lower than in the past. Therefore, stress is unlikely to occur at the interface between the electrode and the solid electrolyte, and peeling or cracking of the electrode hardly occurs.
【００１２】また、請求項２によれば、粒子径が５μｍ
以下の導電性材料粉末と有機高分子を混ぜて焼成するこ
とにより、粒子径の小さな導電性材料粉末が凝集して、
電極ペーストを焼き付けする前の段階で多孔質性の導電
性材料粉末が得られ、焼き付けによる更なる凝縮を防ぐ
ことができる。According to claim 2, the particle diameter is 5 μm.
By mixing and firing the following conductive material powder and organic polymer, the conductive material powder with a small particle size is aggregated,
A porous conductive material powder is obtained at a stage before baking the electrode paste, and further condensation due to baking can be prevented.
【００１３】また、請求項３によれば、多孔質電極は、
粒子径が５μｍ以下の粒子が凝集し、かつ、気孔を有す
ることにより、例えば、燃料電池においては、電極の見
掛けの面積当たりの電極反応の起こる反応面積が大きく
なり、燃料電池の性能が向上する。According to claim 3, the porous electrode is
By aggregating particles having a particle diameter of 5 μm or less and having pores, for example, in a fuel cell, a reaction area where an electrode reaction takes place per apparent area of an electrode becomes large, and the performance of the fuel cell is improved. .
【００１４】[0014]
【実施例】以下、本発明の実施例につき、図面を参照し
て説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１５】（実施例１）まず、本発明を固体電解質型
燃料電池の空気極に実施した。(Example 1) First, the present invention was applied to the air electrode of a solid oxide fuel cell.
【００１６】空気極材である粒径約０．５μｍのＬａＭ
ｎＯ3 （ランタンマンガナイト）粉末に対し、有機高分
子である粒径約１μｍの球状セルロース粉末を、２０〜
４０ｗｔ％加えてボールミルで混合し、これを１１００
℃で焼成して多孔質性の導電性材料粉末を得た。LaM having a particle size of about 0.5 μm, which is an air electrode material
20 to 20 g of spherical cellulose powder having a particle diameter of about 1 μm, which is an organic polymer, is added to nO 3 (lanthanum manganite) powder.
Add 40 wt% and mix with a ball mill.
The powder was fired at ℃ to obtain a porous conductive material powder.
【００１７】これにポリビニルブチラール系の結合材と
エタノールとトルエンとを混合した溶剤、及び気孔を作
るための有機高分子である粒径約１μｍの球状セルロー
ス粉末を、導電性材料粉末に対し５〜１５ｗｔ％加えて
空気極ペーストとした。A solvent obtained by mixing a polyvinyl butyral binder with ethanol and toluene, and a spherical cellulose powder having a particle size of about 1 μm, which is an organic polymer for forming pores, are added to the conductive material powder in an amount of 5 to 5. 15 wt% was added to make an air electrode paste.
【００１８】これを電解質であるＹＳＺ（イットリア安
定化ジルコニア）基板の一方の面に塗布して、１２００
℃で焼き付けて空気極とした。そして、この基板の反対
側の面には、多孔質性のＰｔ（白金）ペ−ストを塗布
し、１０００℃で焼き付けて燃料極とした。This is applied to one surface of a YSZ (yttria-stabilized zirconia) substrate which is an electrolyte, and 1200
It was baked at ℃ to make an air electrode. Then, a porous Pt (platinum) paste was applied to the opposite surface of the substrate and baked at 1000 ° C. to form a fuel electrode.
【００１９】そして、電極を焼き付けた状態を、目視と
走査型電子顕微鏡により確認したが、電極が固体電解質
から剥離しておらず、また、電極内部に亀裂も生じてい
なかった。The state in which the electrodes were baked was confirmed visually and by a scanning electron microscope. The electrodes were not peeled from the solid electrolyte and no cracks were formed inside the electrodes.
【００２０】（比較例１）次に、実施例１との比較を行
うべく、空気極材である粒径約０．５μｍのＬａＭｎＯ
3 （ランタンマンガナイト）粉末に、ポリビニルブチラ
ール系の結合材とエタノールとトルエンとを混合した溶
剤、及び気孔を作るための有機高分子である粒径約１μ
ｍの球状セルロース粉末を、導電性材料粉末に対し５〜
１５ｗｔ％加えて空気極ペーストとした。これをＹＳＺ
（イットリア安定化ジルコニア）基板に塗布し、１２０
０℃で焼き付けて空気極とした。そして、この基板の反
対側の面には実施例１と同様に、燃料極として多孔質性
のＰｔ（白金）ペーストを塗布して、１０００℃で焼き
付けたものを準備した。Comparative Example 1 Next, in order to make a comparison with Example 1, LaMnO having a particle size of about 0.5 μm, which is an air electrode material, is used.
3 (lanthanum manganite) powder mixed with polyvinyl butyral binder and ethanol and toluene, and organic polymer to create pores
The spherical cellulose powder of m is 5 to the conductive material powder.
15 wt% was added to make an air electrode paste. This is YSZ
(Yttria-stabilized zirconia) coated on the substrate, 120
It baked at 0 degreeC and was set as the air electrode. Then, in the same manner as in Example 1, a porous Pt (platinum) paste was applied as a fuel electrode to the surface on the opposite side of this substrate, and the one baked at 1000 ° C. was prepared.
【００２１】実施例１と比較例１で得られた試料を水銀
ポロシメータで測定して、空気極の気孔率（空気極の体
積に占める気孔体積の割合）が３０％で、気孔径分布が
同じである実施例１と比較例１の各試料について、１０
００℃で発電を行った。なお、気孔率３０％は多孔質体
が最良特性を示す値として一般に知られているものであ
る。The samples obtained in Example 1 and Comparative Example 1 were measured with a mercury porosimeter, and the porosity of the air electrode (the ratio of the pore volume to the volume of the air electrode) was 30% and the pore size distribution was the same. 10 for each sample of Example 1 and Comparative Example 1
Power was generated at 00 ° C. The porosity of 30% is generally known as a value at which the porous body exhibits the best characteristics.
【００２２】図１は実施例１と比較例１について、各試
料の電流密度と端子電圧を測定した装置の回路図であ
る。燃料極１と空気極３が固体電解質膜２を挟んで発電
部４を構成し、前記各極から燃料電池の運転温度に耐え
るＰｔ線５を引き出して、電圧計６及び可変抵抗器７を
接続した電流計８に、それぞれ接続した。Ｐｔ線５と発
電部４の各極が接続されている箇所は、運転温度で耐熱
気密性に優れたアルミナ管９で覆っている。FIG. 1 is a circuit diagram of an apparatus for measuring the current density and the terminal voltage of each sample in Example 1 and Comparative Example 1. The fuel electrode 1 and the air electrode 3 constitute the power generation unit 4 with the solid electrolyte membrane 2 sandwiched therebetween, and the Pt wire 5 that withstands the operating temperature of the fuel cell is drawn out from each of the electrodes, and the voltmeter 6 and the variable resistor 7 are connected. The respective ammeters 8 were connected to each other. The place where the Pt wire 5 and each pole of the power generation unit 4 are connected is covered with an alumina tube 9 having excellent heat resistance and airtightness at the operating temperature.
【００２３】図２はこれにより測定した電流密度と端子
電圧の比較特性図である。そして、この電流密度と端子
電圧の特性の比較から、本発明により空気極の性能が改
善されて、発電能力が向上したことがわかる。FIG. 2 is a comparative characteristic diagram of the current density and the terminal voltage measured by this. From the comparison of the characteristics of the current density and the terminal voltage, it can be seen that the performance of the air electrode was improved and the power generation capacity was improved by the present invention.
【００２４】（実施例２）次に、本発明を固体電解質型
燃料電池の燃料極に実施した。Example 2 Next, the present invention was applied to the fuel electrode of a solid oxide fuel cell.
【００２５】燃料極材である粒径約０．５μｍのＮｉＯ
（酸化ニッケル）粉末及び粒径約０．５μｍのＹＳＺ
（イットリア安定化ジルコニア）粉末に対し、有機高分
子である粒径約１μｍの球状セルロース粉末を、２０〜
４０ｗｔ％加えてボールミルで混合し、これを９００℃
で焼成して、多孔質性の導電性材料粉末を得た。NiO having a particle size of about 0.5 μm, which is a fuel electrode material
(Nickel oxide) powder and YSZ with a particle size of about 0.5 μm
For (yttria-stabilized zirconia) powder, 20 to 20 parts of spherical cellulose powder, which is an organic polymer, having a particle size of about 1 μm is used.
Add 40 wt% and mix with a ball mill.
Was fired to obtain a porous conductive material powder.
【００２６】これにポリビニルブチラール系の結合材と
エタノールとトルエンとを混合した溶剤、及び気孔を作
るための有機高分子である粒径約１μｍの球状セルロー
ス粉末を、導電性材料粉末に対し５〜１５ｗｔ％加えて
燃料極ペーストとした。A solvent in which a polyvinyl butyral-based binder is mixed with ethanol and toluene, and a spherical cellulose powder having a particle size of about 1 μm, which is an organic polymer for forming pores, are added to the conductive material powder in an amount of 5 to 5. 15 wt% was added to make a fuel electrode paste.
【００２７】これを電解質であるＹＳＺ（イットリア安
定化ジルコニア）基板の一方の面に塗布して１４００℃
で焼き付けた。そして、この基板の反対側の面には、多
孔質性のＰｔ（白金）ペ−ストを塗布し、１０００℃で
焼き付けて空気極とした。This is applied to one surface of a YSZ (yttria-stabilized zirconia) substrate which is an electrolyte, and the temperature is 1400 ° C.
Burned in. Then, a porous Pt (platinum) paste was applied to the opposite surface of the substrate and baked at 1000 ° C. to form an air electrode.
【００２８】そして、電極を焼き付けた状態を、目視と
走査型電子顕微鏡により確認したが、電極が固体電解質
から剥離しておらず、また、電極内部に亀裂も生じてい
なかった。The baked state of the electrode was confirmed visually and by a scanning electron microscope. The electrode was not peeled off from the solid electrolyte and no crack was formed inside the electrode.
【００２９】（比較例２）次に、実施例２との比較を行
うべく、燃料極材である粒径約０．５μｍのＮｉＯ（酸
化ニッケル）粉末及び粒径約０．５μｍのＹＳＺ（イッ
トリア安定化ジルコニア）粉末に、ポリビニルブチラー
ル系の結合材とエタノールとトルエンとを混合した溶
剤、及び気孔を作るための有機高分子である粒径約１μ
ｍの球状セルロース粉末を、導電性材料粉末に対して５
〜１５ｗｔ％加えて燃料極ペーストとした。これをＹＳ
Ｚ（イットリア安定化ジルコニア）基板に塗布して１４
００℃で焼き付け、これに実施例２と同様に、空気極と
して多孔質性のＰｔ（白金）ペーストを塗布して、１０
００℃で焼き付けたものを準備した。(Comparative Example 2) Next, in order to make a comparison with Example 2, NiO (nickel oxide) powder having a particle size of about 0.5 μm and YSZ (yttria) having a particle size of about 0.5 μm are used as fuel electrode materials. Stabilized zirconia) powder, polyvinyl butyral type binder and solvent which mixed ethanol and toluene, and a particle size of about 1μ which is an organic polymer for forming pores.
m spherical cellulose powder to the conductive material powder 5
-15 wt% was added to make a fuel electrode paste. This is YS
Apply 14 to Z (yttria-stabilized zirconia) substrate
Baking at 00 ° C., and applying a porous Pt (platinum) paste as an air electrode to this as in Example 2, and applying 10
The thing baked at 00 degreeC was prepared.
【００３０】実施例２と比較例２で得られた試料を水銀
ポロシメータで測定し、燃料極の気孔率が３０％で気孔
径分布が同じである実施例２と比較例２の各試料につい
て、１０００℃で発電を行った。The samples obtained in Example 2 and Comparative Example 2 were measured by a mercury porosimeter, and the respective samples of Example 2 and Comparative Example 2 in which the porosity of the fuel electrode was 30% and the pore size distribution was the same, Power was generated at 1000 ° C.
【００３１】図１の測定回路にて、実施例２と比較例２
の各試料の電流密度と端子電圧を測定し、図３に測定し
た電流密度と端子電圧の比較特性図を示した。In the measurement circuit of FIG. 1, Example 2 and Comparative Example 2
The current density and terminal voltage of each sample were measured, and FIG. 3 shows a comparison characteristic diagram of the measured current density and terminal voltage.
【００３２】そして、この電流密度と端子電圧の特性の
比較から、本発明により、空気極の性能が改善されてお
り、発電能力が向上したことがわかる。From the comparison of the characteristics of the current density and the terminal voltage, it is understood that the performance of the air electrode is improved and the power generation capacity is improved by the present invention.
【００３３】[0033]
【発明の効果】本発明によれば、粒子径５μｍ以下の粒
子が凝集した、気孔を有する多孔質性の導電性材料粉末
が容易に得られ、例えば、これを調製して固体電解質に
焼き付けた多孔質電極は、電極が固体電解質から剥離し
たり、電極内部に亀裂が生じることもない。また、粒子
の小さい電極材を用いるため、電極の見掛けの面積当た
りの電極反応の起こる反応面積が大きくなり、例えば、
電流・電圧特性が改善されて燃料電池の性能が向上する
という効果を奏するものである。According to the present invention, a porous conductive material powder having pores in which particles having a particle diameter of 5 μm or less are aggregated can be easily obtained. For example, this is prepared and baked into a solid electrolyte. The porous electrode does not peel off from the solid electrolyte or crack inside the electrode. Moreover, since an electrode material having small particles is used, the reaction area where the electrode reaction takes place per apparent area of the electrode becomes large, and for example,
The current / voltage characteristics are improved and the performance of the fuel cell is improved.
【００３４】そして、本発明を固体電解質型燃料電池の
空気極と燃料極に用いて発電能力が向上したように、例
えば、ガスセンサー、湿度センサー等の多孔質体構造の
電極に用いることによっても、その性能を向上させるこ
とができる。As in the case where the present invention is used for the air electrode and the fuel electrode of a solid oxide fuel cell to improve the power generation capacity, it can be used for an electrode having a porous structure such as a gas sensor and a humidity sensor. , Its performance can be improved.
【図１】本発明の実施例１，２及び比較例１，２で得ら
れた各試料の電流密度と端子電圧の測定回路図。FIG. 1 is a circuit diagram for measuring the current density and terminal voltage of each sample obtained in Examples 1 and 2 of the present invention and Comparative Examples 1 and 2.
【図２】本発明の実施例１と比較例１で得られた各試料
の電流密度と端子電圧の特性図。FIG. 2 is a characteristic diagram of current density and terminal voltage of each sample obtained in Example 1 of the present invention and Comparative Example 1.
【図３】本発明の実施例２と比較例２で得られた各試料
の電流密度と端子電圧の特性図。FIG. 3 is a characteristic diagram of current density and terminal voltage of each sample obtained in Example 2 of the present invention and Comparative Example 2.
１ 燃料極 ２ 固体電解質 ３ 空気極 ４ 発電部 ５ Ｐｔ（白金）線 ６ 電圧計 ７ 可変抵抗器 ８ 電流計 ９ アルミナ管 1 Fuel Electrode 2 Solid Electrolyte 3 Air Electrode 4 Power Generation Section 5 Pt (Platinum) Wire 6 Voltmeter 7 Variable Resistor 8 Ammeter 9 Alumina Tube
Claims (3)
つ、気孔を有することを特徴とする多孔質性の導電性材
料粉末。1. A porous conductive material powder, wherein particles having a particle diameter of 5 μm or less are aggregated and have pores.
有機高分子を混ぜて焼成することを特徴とする多孔質性
の導電性材料粉末の製造方法。2. A method for producing a porous conductive material powder, comprising mixing a conductive material powder having a particle diameter of 5 μm or less and an organic polymer and firing the mixture.
り、かつ、気孔を有することを特徴とする多孔質電極。3. A porous electrode in which particles having a particle diameter of 5 μm or less are aggregated and have pores.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04819194A JP3533694B2 (en) | 1994-03-18 | 1994-03-18 | Porous conductive material powder, method for producing the same, and method for producing fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04819194A JP3533694B2 (en) | 1994-03-18 | 1994-03-18 | Porous conductive material powder, method for producing the same, and method for producing fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07262819A true JPH07262819A (en) | 1995-10-13 |
| JP3533694B2 JP3533694B2 (en) | 2004-05-31 |
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ID=12796504
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04819194A Expired - Lifetime JP3533694B2 (en) | 1994-03-18 | 1994-03-18 | Porous conductive material powder, method for producing the same, and method for producing fuel cell |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006046624A1 (en) * | 2004-10-29 | 2006-05-04 | The Tokyo Electric Power Company, Incorporated | Powdery metal oxide mother particles, powdery metal oxide child particles, process for producing powdery metal oxide particles, powdery composite particles, and electrode for solid oxide fuel cell |
| JP2006127951A (en) * | 2004-10-29 | 2006-05-18 | Tokyo Electric Power Co Inc:The | Powdered composite particles and method for producing the same |
| JP2011514644A (en) * | 2008-03-18 | 2011-05-06 | テクニカル ユニヴァーシティー オブ デンマーク | All-ceramic solid oxide battery |
-
1994
- 1994-03-18 JP JP04819194A patent/JP3533694B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006046624A1 (en) * | 2004-10-29 | 2006-05-04 | The Tokyo Electric Power Company, Incorporated | Powdery metal oxide mother particles, powdery metal oxide child particles, process for producing powdery metal oxide particles, powdery composite particles, and electrode for solid oxide fuel cell |
| JP2006127951A (en) * | 2004-10-29 | 2006-05-18 | Tokyo Electric Power Co Inc:The | Powdered composite particles and method for producing the same |
| JP2011514644A (en) * | 2008-03-18 | 2011-05-06 | テクニカル ユニヴァーシティー オブ デンマーク | All-ceramic solid oxide battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3533694B2 (en) | 2004-05-31 |
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