JP2815901B2 - Internal reforming molten carbonate fuel cell - Google Patents
Internal reforming molten carbonate fuel cellInfo
- Publication number
- JP2815901B2 JP2815901B2 JP1156221A JP15622189A JP2815901B2 JP 2815901 B2 JP2815901 B2 JP 2815901B2 JP 1156221 A JP1156221 A JP 1156221A JP 15622189 A JP15622189 A JP 15622189A JP 2815901 B2 JP2815901 B2 JP 2815901B2
- Authority
- JP
- Japan
- Prior art keywords
- plate
- fuel cell
- nickel
- internal reforming
- gas
- 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.)
- Expired - Fee Related
Links
- 238000002407 reforming Methods 0.000 title claims description 18
- 239000000446 fuel Substances 0.000 title claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title description 4
- 239000007789 gas Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
-
- 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
- Fuel Cell (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
Description
【発明の詳細な説明】 （イ） 産業上の利用分野 本発明は内部改質型溶融炭酸塩燃料電池に関するもの
である。The present invention relates to an internal reforming type molten carbonate fuel cell.
（ロ） 従来の技術 溶融炭酸塩燃料電池は作動温度が約650℃の高温であ
るので、この電池反応熱を利用して改質反応を電池内で
行うことができる。この場合直接内部改質型電池では、
アノード側ガス通路に改質触媒を設置し、天然ガスとス
チームとの混合ガスを導入することにより改質反応を行
わせ、得られた水素リッチガスを燃料ガスとして使用す
る。(B) Conventional technology Since the operating temperature of a molten carbonate fuel cell is as high as about 650 ° C., a reforming reaction can be performed in the cell by using the heat of the reaction of the cell. In this case, in the direct internal reforming type battery,
A reforming catalyst is installed in the anode gas passage, and a reforming reaction is performed by introducing a mixed gas of natural gas and steam, and the obtained hydrogen-rich gas is used as a fuel gas.
従来のこの改質触媒はアノード側ガス通路に配置した
コルゲート板に直接保持されていた。このため隣接する
アノード極から浸み出してくるもしくは蒸気となって飛
散してくる電解質が改質触媒に付着して触媒活性を低下
させるという問題があった。This conventional reforming catalyst was directly held on a corrugated plate disposed in the anode gas passage. For this reason, there has been a problem that the electrolyte leached from the adjacent anode electrode or scattered as vapor adheres to the reforming catalyst and reduces the catalytic activity.
（ハ） 発明が解決しようとする課題 本発明は電解質による改質触媒の劣化を抑制し、改質
特性の改善と電池寿命の向上を図るものである。(C) Problems to be Solved by the Invention The present invention is intended to suppress the deterioration of the reforming catalyst due to the electrolyte, and to improve the reforming characteristics and the battery life.
（ニ） 課題を解決するための手段 本発明は電解質板を介して対向するアノード極とカソ
ード極の各極背面に、ガス分離板によって各極反応ガス
通路を形成し、前記アノード側ガス通路に配置したコル
ゲート板に、改質触媒が内設され、且つニッケルもしく
はニッケル合金の薄板が螺旋状もしくは筒状に巻回して
構成された、弾力を有する有孔筒体を設置せしめてなる
ものである。(D) Means for Solving the Problems In the present invention, each electrode reaction gas passage is formed by a gas separation plate on the back surface of each of the anode and cathode electrodes opposed to each other with an electrolyte plate interposed therebetween. A resilient perforated cylindrical body in which a reforming catalyst is internally provided and a thin plate of nickel or a nickel alloy is spirally or cylindrically wound is disposed on the disposed corrugated plate. .
（ホ） 作用 本発明ではアノード極に浸み出した電解質やその蒸気
がコルゲート板に達しても、改質触媒が有孔筒体内に配
置されているので、電解質との接触を防止して触媒能の
劣化を抑制することができるとともに筒体が電解質に対
してぬれ性がなく高温ガス雰囲気下優れた安定性を有す
るニッケルもしくはニッケル合金の薄板で形成されてい
るので、ガスの流入流出に支障なくガス通路内における
差圧を増大するおそれもない。(E) Function In the present invention, even if the electrolyte or its vapor leached into the anode electrode reaches the corrugated plate, the reforming catalyst is arranged in the perforated cylinder, so that the catalyst is prevented from contacting with the electrolyte to prevent the catalyst from contacting the electrolyte. Since the cylinder is made of a thin plate of nickel or nickel alloy, which can suppress the deterioration of performance and has excellent stability in a high-temperature gas atmosphere without wettability to the electrolyte, it prevents gas inflow and outflow. Also, there is no possibility of increasing the differential pressure in the gas passage.
加えて、有孔筒体が薄板を螺旋状もしくは筒状に巻回
して構成さえるので、添え自身の弾力で改質触媒をコル
ゲート板に強固に支持することができる。In addition, since the perforated cylindrical body is formed by winding a thin plate into a spiral or cylindrical shape, the reforming catalyst can be firmly supported on the corrugated plate by the elasticity of the attachment itself.
（ヘ） 実施例 第１図は本発明電池の単セル模式断面図で、溶融炭酸
塩を含有するセラミックス電解質板（１）の両面に、ニ
ッケル合金焼結体よりなるアノード極（２）とリチウム
化酸化ニッケル燒結体よるなるカソード極（３）とを夫
々密接し、これら各極背面にガス通路を形成するガス分
離板〔第１図ではガス通路枠（４）（５）〕が電解質板
（１）の周辺との間でウエットシール部（６）を構成す
る。(F) Example FIG. 1 is a schematic cross-sectional view of a single cell of the battery of the present invention, in which an anode electrode (2) made of a nickel alloy sintered body and lithium are provided on both surfaces of a ceramic electrolyte plate (1) containing a molten carbonate. A cathode separator (3) made of a nickel oxide sinter is in close contact with each other, and a gas separation plate (in FIG. 1, gas passage frames (4) and (5) in FIG. 1) for forming a gas passage is formed on the back of each electrode. A wet seal portion (6) is formed with the periphery of (1).
各ガス通路枠（４）（５）内には、夫々集電板（７）
（８）とコルゲート極（９）（10）を配置しているが、
カソード極の集電板（８）及びコルゲート板（10）は、
いづれもステンレス鋼製であるに対し、アノード側の集
電板（７）はニッケル製、コルゲート板（９）はニッケ
ル合金（例えばインコネル）からなる。又ガス通路枠
（４）（５）はいづれもステンレス鋼製であるが、アノ
ード側通路枠（４）の内面にはニッケル薄板（11）が設
置されている。In each gas passage frame (4) (5), a current collector (7)
(8) and corrugated poles (9) and (10)
The current collector plate (8) and the corrugated plate (10) of the cathode
Both are made of stainless steel, whereas the current collector plate (7) on the anode side is made of nickel, and the corrugated plate (9) is made of a nickel alloy (for example, Inconel). Each of the gas passage frames (4) and (5) is made of stainless steel, and a nickel thin plate (11) is provided on the inner surface of the anode-side passage frame (4).
改質触媒（12）は、径1mm、長さ2mmの円柱状Ni/MgO系
市販触媒を用い、これを複数個あらかじめニッケルもし
くはニッケル合金製の有孔筒体（13）内に収納され、こ
の筒体（13）がアノード側コルゲート板（９）に嵌着保
持される。筒体（13）は厚み約0.1mmのニッケル薄板を
第２図に示すよう螺旋状に巻き加工したものを用いる
か、同厚のニッケルパンチングメタルを第３図に示すよ
う筒状に巻き加工したものを用いる。いずれもそれ自体
の弾力でコルゲート板（９）に強固に設置される。As the reforming catalyst (12), a cylindrical Ni / MgO-based commercial catalyst having a diameter of 1 mm and a length of 2 mm is used, and a plurality of these are housed in advance in a perforated cylindrical body (13) made of nickel or a nickel alloy. The cylindrical body (13) is fitted and held on the anode-side corrugated plate (9). As the cylindrical body (13), a nickel thin plate having a thickness of about 0.1 mm is spirally wound as shown in FIG. 2, or a nickel punched metal having the same thickness is rolled into a cylindrical shape as shown in FIG. Use something. Each is firmly installed on the corrugated plate (9) by its own elasticity.
寸法250cm2の極板を用いて組立てた単セルについて、
所定条件で昇温し650℃となった時点でスチームと天然
ガスの混合原料ガスをアノードガス通路枠（４）内に導
入し、改質触媒（12）で水素リッチガスに改質した。こ
れを燃料ガスとし、カソードガス通路枠（５）内に供給
した空気と炭酸ガスとの混合ガスとの間で電池反応を行
った。電池特性は電流密度150mA/cm2以下で特性が安定
した後測定した。これによると本発明電池と従来電池と
は、初期特性は同等であるが、長期特性は従来電池が著
しく低下するに対し、本発明電池では安定に推移してい
ることが確認された。For a single cell assembled using a 250 cm 2 electrode plate,
When the temperature was raised to 650 ° C. under predetermined conditions, a mixed raw material gas of steam and natural gas was introduced into the anode gas passage frame (4), and reformed into a hydrogen-rich gas by the reforming catalyst (12). Using this as a fuel gas, a cell reaction was performed between a mixed gas of air and carbon dioxide gas supplied into the cathode gas passage frame (5). The battery characteristics were measured after the characteristics were stabilized at a current density of 150 mA / cm 2 or less. According to this, it was confirmed that the battery of the present invention and the conventional battery had the same initial characteristics, but the long-term characteristics of the battery of the present invention were remarkably deteriorated, whereas the batteries of the present invention were stable.
（ト） 発明の効果 本発明によれば改質触媒を直線コルゲート板に支持す
ることなく、ニッケルもしくはニッケル合金製の有孔筒
体内に収納して間接的に支持されているので、電解質や
その蒸気がコルゲート板に達しても電解質との接触が防
止され、触媒能の劣化を抑制することができる。又有孔
筒体が薄板を螺旋状もしくは筒状に巻回して構成される
ので、それ自身の弾力で改質触媒をコルゲート板に強固
に支持することができるなどの特長を有し、直接式内部
改質型電池の特性改善及び寿命向上が達成される。(G) Effect of the Invention According to the present invention, the reforming catalyst is stored in a perforated cylinder made of nickel or nickel alloy and is indirectly supported without being supported by the linear corrugated plate. Even if the vapor reaches the corrugated plate, contact with the electrolyte is prevented, and deterioration of the catalytic ability can be suppressed. In addition, since the perforated cylindrical body is formed by winding a thin plate into a spiral shape or a cylindrical shape, it has the advantage that the reforming catalyst can be firmly supported on the corrugated plate by its own elasticity. Improvements in the characteristics and life of the internal reforming battery are achieved.
第１図は本発明電池における単セルの模式的断面図、第
２図は同上の要部斜面図、第３図は同じく他実施例によ
る要部斜面図である。 1:電解質板、2:アノード極、3:カソード極、4,5:ガス通
路枠、7,8:集電板、9,10:コルゲート板、12:改質触媒、
13:有孔筒体。FIG. 1 is a schematic cross-sectional view of a single cell of the battery of the present invention, FIG. 2 is a perspective view of a main part of the same, and FIG. 3 is a perspective view of a main part according to another embodiment. 1: electrolyte plate, 2: anode electrode, 3: cathode electrode, 4, 5: gas passage frame, 7, 8: current collector plate, 9, 10: corrugated plate, 12: reforming catalyst,
13: Perforated cylinder.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−296655（ＪＰ，Ａ) 実開 昭63−99761（ＪＰ，Ｕ) (58)調査した分野(Int.Cl.6，ＤＢ名) H01M 8/00 - 8/24──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-296655 (JP, A) JP-A-63-99761 (JP, U) (58) Fields investigated (Int. Cl. 6 , DB name) H01M 8/00-8/24
Claims (1)
ソード極の各極背面に、ガス分離板によって各極反応ガ
ス通路を形成し、前記アノード側ガス通路に配置したコ
ルゲート板に、改質触媒が内設され、且つニッケルもし
くはニッケル合金の薄板が螺旋状もしくは筒状に巻回し
て構成された、弾力を有する有孔筒体を設置せしめてな
ることを特徴とする内部改質型溶融炭酸塩燃料電池。1. A gas separation plate is formed on each electrode back surface of an anode and a cathode facing each other via an electrolyte plate to form a reaction gas passage for each electrode. Internal reforming type molten carbonic acid characterized by being provided with a resilient perforated cylindrical body having a catalyst provided therein and formed by winding a thin plate of nickel or nickel alloy into a spiral or cylindrical shape. Salt fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1156221A JP2815901B2 (en) | 1989-06-19 | 1989-06-19 | Internal reforming molten carbonate fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1156221A JP2815901B2 (en) | 1989-06-19 | 1989-06-19 | Internal reforming molten carbonate fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0322364A JPH0322364A (en) | 1991-01-30 |
| JP2815901B2 true JP2815901B2 (en) | 1998-10-27 |
Family
ID=15623005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1156221A Expired - Fee Related JP2815901B2 (en) | 1989-06-19 | 1989-06-19 | Internal reforming molten carbonate fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2815901B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61296655A (en) * | 1985-06-26 | 1986-12-27 | Mitsubishi Electric Corp | Molten carbonate type fuel cell |
| JPH0615404Y2 (en) * | 1986-12-19 | 1994-04-20 | 三菱電機株式会社 | Internal reforming fuel cell |
-
1989
- 1989-06-19 JP JP1156221A patent/JP2815901B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0322364A (en) | 1991-01-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |