JPH0349156A - Fuel electrode for solid electrolyte fuel cell - Google Patents
Fuel electrode for solid electrolyte fuel cellInfo
- Publication number
- JPH0349156A JPH0349156A JP1182592A JP18259289A JPH0349156A JP H0349156 A JPH0349156 A JP H0349156A JP 1182592 A JP1182592 A JP 1182592A JP 18259289 A JP18259289 A JP 18259289A JP H0349156 A JPH0349156 A JP H0349156A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- particles
- nickel
- fuel electrode
- electrode
- 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.)
- Pending
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims description 59
- 239000000463 material Substances 0.000 abstract description 12
- 238000003487 electrochemical reaction Methods 0.000 abstract description 9
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 abstract description 9
- 230000008646 thermal stress Effects 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 abstract description 2
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、固体電解質燃料電池用燃料電極の改良に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to improvements in fuel electrodes for solid electrolyte fuel cells.
［従来の技術］
従来、固体電解質燃料電池の燃料電極としては下記のよ
うなものが知られている。[Prior Art] Conventionally, the following fuel electrodes for solid electrolyte fuel cells are known.
■ニッケル粒子１により板状に成形した多孔−質ニッケ
ル焼結板２を用いたもの（第４図図示）。(2) A device using a porous sintered nickel plate 2 formed into a plate shape using nickel particles 1 (as shown in FIG. 4).
■ニッケル粒子１とジルコニアなどのセラミックス粒子
３を混合、焼結した多孔質ニッケルジルフニアサーメッ
ト焼結板を用いたもの（第５図図示）。(2) A porous nickel-zilfnia cermet sintered plate made by mixing and sintering nickel particles 1 and ceramic particles 3 such as zirconia (as shown in Figure 5).
■上記■と同じ材料で、かつニッケル粒子１とセラミッ
クス粒子３の構成比を変化させて傾斜機能材４としたも
の（第６図図示）。ここで、セパレート側（上側）はニ
ッケル粒子１が多く存在し、電解質側（下側）はセラミ
ックス粒子３が多く存在する。(2) A functionally gradient material 4 made of the same material as (2) above, but with a different composition ratio of nickel particles 1 and ceramic particles 3 (as shown in Figure 6). Here, many nickel particles 1 exist on the separate side (upper side), and many ceramic particles 3 exist on the electrolyte side (lower side).
［発明が解決しようとする課題］
しかしながら、従来の燃料電極によれば、以下に述べる
問題点を有する。[Problems to be Solved by the Invention] However, the conventional fuel electrode has the following problems.
イ）上記■の場合二ニッケル粒子１のみで燃料局を構成
すると、電気化学反応及び導電性に優れている。しかし
、線膨張係数が固体電解質材料（通常、イツトリア安定
化ジルコニア）よりかなり大きいため、熱応力により固
体電解質または電極が破壊される。b) In the case of (2) above, if the fuel station is made up of only two nickel particles 1, the electrochemical reaction and conductivity will be excellent. However, because the coefficient of linear expansion is much larger than the solid electrolyte material (usually yttria-stabilized zirconia), thermal stress can destroy the solid electrolyte or electrode.
口）上記■の場合；ニッケル粒子１とセラミックス粒子
３を適当な比率で混合した場合には、線膨張係数を固体
電解質材料と近似させる事ができ、熱応力による破壊を
防止できる。しかし、セラミックス粒子３が分散してい
るため、電極としての導電性が低下（ジルコニアなど絶
縁性のため）するとともに、ニッケル粒子の表面積が減
少し、電気化学反応が低下する。(2) Case above: When nickel particles 1 and ceramic particles 3 are mixed in an appropriate ratio, the coefficient of linear expansion can be approximated to that of the solid electrolyte material, and destruction due to thermal stress can be prevented. However, since the ceramic particles 3 are dispersed, the conductivity as an electrode is reduced (due to insulating properties such as zirconia), the surface area of the nickel particles is reduced, and the electrochemical reaction is reduced.
ハ）上記■の場合；上記口）と同様な問題点を有する。C) Case (2) above; has the same problem as (2) above.
本発明は上記事情に鑑みてなされたもので、電気化学反
応及び導電性に優れているとともに、熱応力により固体
電解質または電極が破壊される事ことを防止しえる固体
電解質燃料電池用燃料電極を提供することを目的とする
。The present invention has been made in view of the above circumstances, and provides a fuel electrode for solid electrolyte fuel cells that has excellent electrochemical reaction and conductivity, and can prevent the solid electrolyte or electrode from being destroyed by thermal stress. The purpose is to provide.
［課題を解決するための手段］
本発明は、表面にニッケル粒子をコーティング本発明に
おいて、上記セラミック粒子としては、通常の固体電解
質材料例えばイツトリア安定化ジルコニア（ＹＳＺ）よ
りも線膨張係数が小さいアルミナ、炭化ケイ素等のセラ
ミック粒子、あるいはＹＳＺそのもの、あるいは部分安
定化ジルコニア等のセラミック粒子が挙げられる。[Means for Solving the Problems] In the present invention, the ceramic particles are coated with nickel particles on the surface, and the ceramic particles are made of alumina, which has a linear expansion coefficient smaller than that of ordinary solid electrolyte materials, such as yttria-stabilized zirconia (YSZ). , ceramic particles such as silicon carbide, YSZ itself, or ceramic particles such as partially stabilized zirconia.
［作用］
本発明によれば、
■セラミックス粒子の表面にニッケル粒子をコーティン
グし、係る粒子を用いて板状に加工しｔ、：構成となっ
Ｃいるため、板材の線膨張係数が上記セラミックス粒子
とニッケル粒子の中間の値となる。従って、板状の燃料
電極と固体電解質材との線膨張係数がマツチし、熱応力
に対して安定した燃料電極が得られる。[Function] According to the present invention, the surface of the ceramic particles is coated with nickel particles, and the particles are processed into a plate shape so that the coefficient of linear expansion of the plate material is equal to that of the ceramic particles. The value is between that of nickel particles and nickel particles. Therefore, the linear expansion coefficients of the plate-shaped fuel electrode and the solid electrolyte material match, and a fuel electrode that is stable against thermal stress can be obtained.
■上記セラミックス粒子の表面は、電気化学反応及び発
生した電流の導電材としての機能を有するニッケル粒子
でコーティングされている。従って、板状に加工された
状態においてもあたかもニッケル粒子がのみで制作した
場合と同様の電気化学反応が期待でき、又導電材として
の機能も十分である。(2) The surfaces of the ceramic particles are coated with nickel particles that function as a conductive material for electrochemical reactions and generated current. Therefore, even when processed into a plate shape, electrochemical reactions similar to those produced using nickel particles alone can be expected, and the material also functions satisfactorily as a conductive material.
■セラミックス粒子の表面のニッケル粒子の同志が焼結
されているため、たとえ上記セラミ・ソクス粒子とニッ
ケル粒子の線膨張係数の差により内部で剥離を生じても
、電極全体の破壊となりにくい。■Since the nickel particles on the surface of the ceramic particles are sintered, even if peeling occurs internally due to the difference in linear expansion coefficient between the ceramic particles and the nickel particles, the entire electrode is unlikely to be destroyed.
■製造の中間工程で顆粒状にすることにより、気孔径の
大きな多孔質板の製作ができ、ガス透過性が向上する。■ By making it into granules during the intermediate manufacturing process, it is possible to produce porous plates with large pore diameters, improving gas permeability.
■製造の中間工程で酸化処理することにより、気孔径の
大きな多孔質板の製作力１でき、ガス透過性が向上する
。(2) By performing oxidation treatment in the intermediate process of manufacturing, it is possible to produce porous plates with large pore diameters, and gas permeability is improved.
以下、本発明の実施例について説明する。Examples of the present invention will be described below.
［実施例１］ 第１図を参照する。[Example 1] Please refer to FIG.
図中の１１は、燃料電極である。この燃料電極１１は、
セラミックス粒子１２の表面にニッケル粒子１３を例え
ばメツキ法等によりコーティングしたものを、板状に成
形し、焼成することにより構成される。ここに、前記セ
ラミックス粒子１２としては、例えばアルミナ粒子を用
いる。このアルミナ粒子の線膨張係数は、固体電解質の
通常の材料であるイツトリア安定化ジルコニアの線膨張
係数より小さい。11 in the figure is a fuel electrode. This fuel electrode 11 is
It is constructed by coating the surfaces of ceramic particles 12 with nickel particles 13 by, for example, a plating method, forming them into a plate shape, and firing them. Here, as the ceramic particles 12, for example, alumina particles are used. The linear expansion coefficient of the alumina particles is smaller than that of yttria-stabilized zirconia, which is a common material for solid electrolytes.
こうした構成の燃料電極によれば、固体電解質の材料よ
り線膨張係数の小さいセラミックス粒子１２の表面にニ
ッケル粒子１３をコーティングし、係る粒子を用いて板
状に加工した構成となっているため、板材の線膨張係数
が上記セラミックス粒子１２とニッケル粒子１３の中間
の値となる。従って、板状の燃料電極１１と固体電解質
材との線膨張係数がマツチし、熱応力に対して安定した
燃料電極１１が得られる。According to the fuel electrode having such a structure, the surface of the ceramic particles 12 having a smaller coefficient of linear expansion than the material of the solid electrolyte is coated with nickel particles 13, and the particles are processed into a plate shape. The coefficient of linear expansion is an intermediate value between the ceramic particles 12 and the nickel particles 13. Therefore, the linear expansion coefficients of the plate-shaped fuel electrode 11 and the solid electrolyte material match, and a fuel electrode 11 that is stable against thermal stress can be obtained.
また、上記セラミックス粒子１２の表面は、電気化学反
応及び発生した電流の導電材としての機能を有するニッ
ケル粒子１３でコーティングされている。従って、板状
に加工された状態においてもあたかもニッケル粒子１３
がのみで制作した場合と同様の電気化学反応が期待でき
、又導電材としての機能も十分である。Furthermore, the surfaces of the ceramic particles 12 are coated with nickel particles 13 that function as a conductive material for electrochemical reactions and generated current. Therefore, even when processed into a plate shape, the nickel particles 13
It can be expected that the same electrochemical reaction as when made with chisel, and it also functions well as a conductive material.
更に、セラミックス粒子１２の表面のニッケル粒子１３
の同志が焼結されているため、たとえ上記セラミックス
粒子１２とニッケル粒子１３の線膨張係数の差により内
部で剥離を生じても、電極全体の破壊となりにくい。Furthermore, nickel particles 13 on the surface of the ceramic particles 12
Since the comrades are sintered, even if peeling occurs internally due to the difference in linear expansion coefficient between the ceramic particles 12 and the nickel particles 13, the entire electrode is unlikely to be destroyed.
［実施例２］ 第２図（Ａ）〜（Ｄ）を参照する。[Example 2] Please refer to FIGS. 2(A) to 2(D).
本実施例２に係る燃料電極１１は、表面にニッケル粒子
１３をコーティングしたセラミックス粒子１２（第２図
（Ａ）図示）を、スラリー状にして仮焼。The fuel electrode 11 according to the second embodiment is made by calcining ceramic particles 12 (shown in FIG. 2(A)) whose surfaces are coated with nickel particles 13 into a slurry.
粉砕（第２図（Ｂ）図示）して顆粒状にした（第２図（
Ｃ）図示）後、成形、焼成（第２図（Ｄ）図示）して製
造される。It was crushed (shown in Figure 2 (B)) and made into granules (Figure 2 (
C) As shown in the figure), the product is then molded and fired (as shown in FIG. 2(D)).
本実施例２に係る燃料電極は、製造の中間工程で顆粒状
にすることにより、気孔径の大きな多孔質板の製作がで
き、ガス透過性が向上する。By forming the fuel electrode according to Example 2 into granules in an intermediate step of manufacturing, a porous plate with a large pore diameter can be manufactured, and gas permeability is improved.
［実施例３］ 第３図（Ａ）〜（Ｄ）を参照する。[Example 3] Please refer to FIGS. 3(A) to 3(D).
本実施例３に係る燃料電極１１は、表面にニッケル粒子
１３をコーティングしたセラミックス粒子」２（第３図
（Ａ）図示）を、酸化処理してニッケル粒子１３の表面
にＮｉ０１１１３ａを形成しく第３図（Ｂ）図示）、更
に板状にした（第３図（Ｃ）図示）後、還元する（第３
図（Ｄ）図示）ことにより製造される。ここに、ニッケ
ル粒子１３は酸化されるとＮｉ０ＩＩ！１３ａにヒビ割
れ１４が生じるが、−皮酸化された部分を還元する事に
よりＮｉｐ＠１３ａ表面が多少微細になる。In the fuel electrode 11 according to the third embodiment, ceramic particles 2 (shown in FIG. 3A) whose surfaces are coated with nickel particles 13 are oxidized to form Ni01113a on the surfaces of the nickel particles 13. Figure (B) shown), further made into a plate shape (Figure 3 (C) shown), and then reduced (3
(D) shown). Here, when the nickel particles 13 are oxidized, they become Ni0II! Cracks 14 occur on the Nip@13a, but the surface of the Nip@13a becomes somewhat finer by reducing the oxidized portion.
本実施例３に係る燃料電極は、製造の中間工程で酸化処
理することにより、気孔径の大きな多孔質板の製作がで
き、ガス透過性が向上する。The fuel electrode according to Example 3 is subjected to oxidation treatment in an intermediate step of manufacturing, so that a porous plate with a large pore diameter can be manufactured, and gas permeability is improved.
なお、上記実施例では、セラミックス粒子としてＹＳＺ
より線膨張係数が小さいアルミナ粒子を用いた場合につ
いて述べたが、これに限らず、ＹＳＺそのものを用いて
もよい。In addition, in the above example, YSZ was used as the ceramic particles.
Although the case has been described in which alumina particles having a smaller coefficient of linear expansion are used, the present invention is not limited to this, and YSZ itself may be used.
［発明の効果］
以上詳述した如く本発明によれば、電気化学反応及び導
電性に優れているとともに、熱応力により固体電解質ま
たは電極が破壊される事ごとを防止しえる固体電解質燃
料電池用燃料電極を提供できる。[Effects of the Invention] As detailed above, the present invention provides a solid electrolyte fuel cell that has excellent electrochemical reactions and conductivity, and can prevent the solid electrolyte or electrode from being destroyed by thermal stress. Can provide fuel electrodes.
第１図は本発明の実施例１に係る燃料電極の説明図、第
２図（Ａ）〜（Ｄ）は本発明の実施例２の燃料電極の製
造方法を工程順に示す説明図、第３図（Ａ）〜（Ｄ）は
本発明の実施例２の燃料電極の製造方法を工程順に示す
説明図、第４図〜第６図は夫々従来の燃料電極の説明図
である。
１１・・・燃料電極、１２・・・セラミックス粒子、１
３・・・ニッケル粒子、１３ａ・・・ＮｉＯ膜。FIG. 1 is an explanatory diagram of a fuel electrode according to Example 1 of the present invention, FIGS. Figures (A) to (D) are explanatory diagrams showing the manufacturing method of a fuel electrode according to Example 2 of the present invention in the order of steps, and Figs. 4 to 6 are explanatory diagrams of conventional fuel electrodes, respectively. 11... Fuel electrode, 12... Ceramic particles, 1
3...Nickel particles, 13a...NiO film.
Claims (1)
子を用いて板状に成形し、焼成してなることを特徴とす
る固体電解質燃料電池用燃料電極。A fuel electrode for a solid electrolyte fuel cell characterized by being formed into a plate shape using ceramic particles coated with nickel particles on the surface and fired.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1182592A JPH0349156A (en) | 1989-07-17 | 1989-07-17 | Fuel electrode for solid electrolyte fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1182592A JPH0349156A (en) | 1989-07-17 | 1989-07-17 | Fuel electrode for solid electrolyte fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0349156A true JPH0349156A (en) | 1991-03-01 |
Family
ID=16120982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1182592A Pending JPH0349156A (en) | 1989-07-17 | 1989-07-17 | Fuel electrode for solid electrolyte fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0349156A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008052991A (en) * | 2006-08-23 | 2008-03-06 | Sanyo Special Steel Co Ltd | Manufacturing method of metallic porous body electrode |
| JP2008524068A (en) * | 2004-12-22 | 2008-07-10 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Pressure system with at least two pressure circuits |
-
1989
- 1989-07-17 JP JP1182592A patent/JPH0349156A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008524068A (en) * | 2004-12-22 | 2008-07-10 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Pressure system with at least two pressure circuits |
| JP2008052991A (en) * | 2006-08-23 | 2008-03-06 | Sanyo Special Steel Co Ltd | Manufacturing method of metallic porous body electrode |
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