JP5262241B2 - Solid oxide fuel cell - Google Patents

Solid oxide fuel cell Download PDF

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JP5262241B2
JP5262241B2 JP2008089626A JP2008089626A JP5262241B2 JP 5262241 B2 JP5262241 B2 JP 5262241B2 JP 2008089626 A JP2008089626 A JP 2008089626A JP 2008089626 A JP2008089626 A JP 2008089626A JP 5262241 B2 JP5262241 B2 JP 5262241B2
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fuel cell
power generation
solid oxide
cell stack
oxide fuel
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JP2009245686A (en
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勝哉 平田
浩之 江藤
直也 村上
剛 原田
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Kansai Electric Power Co Inc
Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Description

本発明は、断熱ハウジング内に燃料電池スタックを収容して構成した固体酸化物形燃料電池に関するものである。   The present invention relates to a solid oxide fuel cell configured by housing a fuel cell stack in a heat insulating housing.

近年、燃料の有する化学エネルギーを直接電気エネルギーに変換する燃料電池は、高効率でクリーンな発電装置として注目されている。特に、固体酸化物形燃料電池は、発電効率が高く、且つ、排熱を有効に利用できるなどの多くの利点を有することから、第三世代の発電用燃料電池として研究開発が進めらている。   In recent years, fuel cells that directly convert chemical energy of fuel into electrical energy have attracted attention as highly efficient and clean power generators. In particular, solid oxide fuel cells have many advantages such as high power generation efficiency and effective use of exhaust heat, and therefore research and development are underway as third-generation fuel cells for power generation. .

この固体酸化物形燃料電池は、酸化物イオン導電体から成る固体電解質層を両側から酸化剤極層（カソード）と燃料極層（アノード）で挟み込んだ積層構造を有し、発電時には、反応用ガスとして酸化剤極層側に酸化剤ガス（酸素) が、また燃料極層側に燃料ガス (Ｈ２、ＣＯ、ＣＨ４等)が供給される。酸化剤極層と燃料極層は、反応用ガスが固体電解質層との界面に到達することができるよう、何れも多孔質の層とされている。 This solid oxide fuel cell has a laminated structure in which a solid electrolyte layer made of an oxide ion conductor is sandwiched between an oxidant electrode layer (cathode) and a fuel electrode layer (anode) from both sides. As gas, oxidant gas (oxygen) is supplied to the oxidant electrode layer side, and fuel gas (H 2 , CO, CH 4, etc.) is supplied to the fuel electrode layer side. The oxidant electrode layer and the fuel electrode layer are both porous layers so that the reaction gas can reach the interface with the solid electrolyte layer.

発電セル内において、酸化剤極層側に供給された酸素は、酸化剤極層内の気孔を通って固体電解質層との界面近傍に到達し、この部分で酸化剤極層から電子を受け取って酸化物イオン（Ｏ２−）にイオン化される。この酸化物イオンは、燃料極層に向かって固体電解質層内を拡散移動する。燃料極層との界面近傍に到達した酸化物イオンは、この部分で、燃料ガスと反応して反応生成物（Ｈ２Ｏ、ＣＯ２等）を生じ、燃料極層に電子を放出する。電極反応で生じた電子は、別ルートの外部負荷にて起電力として取り出すことができる。 In the power generation cell, oxygen supplied to the oxidant electrode layer side passes through pores in the oxidant electrode layer and reaches the vicinity of the interface with the solid electrolyte layer, and receives electrons from the oxidant electrode layer in this part. It is ionized to oxide ions (O 2− ). The oxide ions diffuse and move in the solid electrolyte layer toward the fuel electrode layer. Oxide ions that have reached the vicinity of the interface with the fuel electrode layer react with the fuel gas at this portion to generate reaction products (H 2 O, CO 2, etc.), and discharge electrons to the fuel electrode layer. Electrons generated by the electrode reaction can be taken out as an electromotive force at an external load on another route.

この種の固体酸化物形燃料電池の中に、運転時に、燃料電池スタックの内部に反応用ガスを供給して発電反応を生じさせると共に、発電反応に使用されなかった残余のガスを、発電セルの外周部より放出するシールレス構造のものがあり、シールレス構造の固体酸化物形燃料電池では、発電セルとセパレータを多数積層して構成した燃料電池スタックを、架台上に多数積み上げて、断熱ハウジング内に収容している（例えば、特許文献１参照）。   In this type of solid oxide fuel cell, during operation, a reaction gas is supplied to the inside of the fuel cell stack to generate a power generation reaction, and the remaining gas not used in the power generation reaction is supplied to the power generation cell. In the case of a solid oxide fuel cell with a sealless structure that discharges from the outer periphery of the fuel cell stack, a number of fuel cell stacks composed of a large number of power generation cells and separators are stacked on a base for heat insulation. It is accommodated in the housing (see, for example, Patent Document 1).

図３は特許文献１に記載されたシールレスタイプの固体酸化物形燃料電池の縦断面図である。図において、符号１は固体酸化物形燃料電池、符号２は断熱ハウジング、符号３は積層方向を縦にして断熱ハウジング２の内部に配設された燃料電池スタックである。   FIG. 3 is a longitudinal sectional view of a sealless type solid oxide fuel cell described in Patent Document 1. In the figure, reference numeral 1 denotes a solid oxide fuel cell, reference numeral 2 denotes a heat insulating housing, and reference numeral 3 denotes a fuel cell stack disposed inside the heat insulating housing 2 with the stacking direction being vertical.

断熱ハウジング２は、ステンレス等の金属製の内部缶体２Ａと外部缶体２Ｂの間に断熱材１８を内装したもので、このハウジング２内に、複数（例えば、８基）の燃料電池スタック３が集合・配置されて、ステンレス等の金属製の架台４１に支持されることで、高出力型の燃料電池モジュールが構成されており、この燃料電池モジュール（固体酸化物形燃料電池１）が支持台４０の上に設置されている。   The heat insulating housing 2 includes a heat insulating material 18 provided between an inner can body 2A and an outer can body 2B made of metal such as stainless steel. A plurality of (for example, eight) fuel cell stacks 3 are provided in the housing 2. Are assembled and arranged, and supported by a metal base 41 such as stainless steel, so that a high output type fuel cell module is configured, and this fuel cell module (solid oxide fuel cell 1) is supported. It is installed on the table 40.

また、ハウジング２内の各燃料電池スタック３には、反応用ガスとして外部から供給される燃料ガスおよび酸化剤ガス（空気）を各燃料電池スタック３内に導入するための燃料ガス供給管１５と酸化剤ガス供給管１６が接続されている。なお、燃料ガス供給管１５は、ハウジング２内において、予熱用の燃料熱交換器３３や改質器３２等を介して各燃料電池スタック３に接続され、酸化剤ガス供給管１６は予熱用の酸化剤ガス熱交換器３４を介して各燃料スタック３に接続されている。   Each fuel cell stack 3 in the housing 2 has a fuel gas supply pipe 15 for introducing a fuel gas and an oxidant gas (air) supplied from the outside as reaction gases into the fuel cell stack 3. An oxidant gas supply pipe 16 is connected. The fuel gas supply pipe 15 is connected to each fuel cell stack 3 in the housing 2 via a preheating fuel heat exchanger 33, a reformer 32, etc., and the oxidant gas supply pipe 16 is used for preheating. The oxidant gas heat exchanger 34 is connected to each fuel stack 3.

燃料電池スタック３は、図４に示すように、固体電解質層４の両面に燃料極層５および酸化剤極層６を配した発電セル７と、燃料極層５の外側の燃料極集電体８と、酸化剤極層６の外側の酸化剤極集電体９と、各集電体８、９の外側のセパレータ１０を順番に多数積層した構造を有する。   As shown in FIG. 4, the fuel cell stack 3 includes a power generation cell 7 in which a fuel electrode layer 5 and an oxidant electrode layer 6 are disposed on both surfaces of a solid electrolyte layer 4, and a fuel electrode current collector outside the fuel electrode layer 5. 8, an oxidant electrode current collector 9 outside the oxidant electrode layer 6, and a large number of separators 10 outside the current collectors 8 and 9 are stacked in order.

ここで、固体電解質層４はイットリアを添加した安定化ジルコニア（ＹＳＺ）等で構成され、燃料極層５はＮｉ等の金属あるいはＮｉ−ＹＳＺ等のサーメットで構成され、空気極層６はＬａＭｎＯ3、ＬａＣｏＯ3等で構成され、燃料極集電体８はＮｉ等のスポンジ状の多孔質焼結金属板で構成され、空気極集電体９はＡｇ等のスポンジ状の多孔質焼結金属板で構成され、セパレータ１０はステンレス等で構成されている。   Here, the solid electrolyte layer 4 is composed of stabilized zirconia (YSZ) to which yttria is added, the fuel electrode layer 5 is composed of a metal such as Ni or a cermet such as Ni—YSZ, and the air electrode layer 6 is LaMnO 3, It is composed of LaCoO3 or the like, the fuel electrode current collector 8 is composed of a sponge-like porous sintered metal plate such as Ni, and the air electrode current collector 9 is composed of a sponge-like porous sintered metal plate such as Ag. The separator 10 is made of stainless steel or the like.

セパレータ１０は、発電セル７間を電気的に接続すると共に、発電セル７に反応用ガスを供給する機能を有し、上記した燃料ガス供給管１５を通して供給される燃料ガスをセパレータ１０の外周面から導入してセパレータ１０の燃料極集電体８に対向するほぼ中央部から吐出する燃料ガス通路１１と、上記した酸化剤ガス供給管１６を通して供給される酸化剤ガスをセパレータ１０の外周面から導入してセパレータ１０の酸化剤極集電体９に対向する面のほぼ中央部から吐出する酸化剤ガス通路１２を備えている。   The separator 10 electrically connects the power generation cells 7 and has a function of supplying a reaction gas to the power generation cells 7. The fuel gas supplied through the fuel gas supply pipe 15 is supplied to the outer peripheral surface of the separator 10. The oxidant gas supplied through the oxidant gas supply pipe 16 and the fuel gas passage 11 that is introduced from the outlet and discharged from the substantially central portion of the separator 10 facing the fuel electrode current collector 8 is supplied from the outer peripheral surface of the separator 10. An oxidant gas passage 12 that is introduced and discharged from substantially the center of the surface of the separator 10 that faces the oxidant electrode current collector 9 is provided.

また、この固体酸化物形燃料電池１は、発電セル７の外周部にガス漏れ防止シールを設けないシールレス構造とされており、運転時には、図４に示すように、燃料ガス通路１１および酸化剤ガス通路１２を通してセパレータ１０の略中心部から発電セル７に向けて吐出される燃料ガスおよび酸化剤ガス（空気）を、発電セル７の外周方向に拡散させながら燃料極層５および酸化剤極層６の全面に良好な分布で行き渡らせて発電反応を生じさせると共に、発電反応で消費されなかった残余のガス（排ガス）を発電セル７の外周部から外に自由に放出するようになっている。
特開２００７−５１３３号公報 In addition, the solid oxide fuel cell 1 has a sealless structure in which a gas leakage prevention seal is not provided on the outer peripheral portion of the power generation cell 7, and during operation, as shown in FIG. The fuel electrode layer 5 and the oxidizer electrode are diffused while diffusing fuel gas and oxidant gas (air) discharged from the substantially central portion of the separator 10 toward the power generation cell 7 through the agent gas passage 12 in the outer peripheral direction of the power generation cell 7. The entire surface of the layer 6 is distributed with a good distribution to generate a power generation reaction, and the remaining gas (exhaust gas) that has not been consumed by the power generation reaction is freely released from the outer periphery of the power generation cell 7 to the outside. Yes.
JP 2007-5133 A

ところで、上述したような従来のシールレスタイプの燃料電池スタック３を有する固体酸化物形燃料電池１においては、燃料電池スタック３の構成部品や架台４１および内部缶体２Ａなどにステンレス等の金属材料を用いているので、燃料電池スタック３の周辺で未反応の燃料ガスが燃焼することにより発生した酸化スケールが、燃料電池スタック３の周辺に浮遊したり堆積したりすることがあった。燃料電池スタック３の周辺に酸化スケールが浮遊したり堆積したりすると、本来、絶縁がとられている部位の絶縁性能が劣化し、短絡や地絡を起こす可能性がある。   By the way, in the solid oxide fuel cell 1 having the conventional sealless type fuel cell stack 3 as described above, a metal material such as stainless steel is used for the components of the fuel cell stack 3, the mount 41, the internal can body 2A, and the like. Therefore, the oxide scale generated by burning unreacted fuel gas around the fuel cell stack 3 sometimes floats or accumulates around the fuel cell stack 3. If the oxide scale floats or accumulates around the fuel cell stack 3, the insulation performance of the portion where the insulation is originally taken deteriorates, which may cause a short circuit or a ground fault.

本発明は、上記事情を考慮し、酸化スケールによる影響を排除できるようにした固体酸化物形燃料電池を提供することを目的とする。   In view of the above circumstances, an object of the present invention is to provide a solid oxide fuel cell that can eliminate the influence of oxide scale.

請求項１の発明の固体酸化物形燃料電池は、発電セルを多数積層して構成した燃料電池スタックを、金属製の架台に載せることで支持して、金属製の内壁を有する断熱ハウジング内に収納し、運転時に、前記燃料電池スタックの内部に反応用ガスを供給して発電反応を生じさせると共に、発電反応に使用されなかった残余のガスを、発電セルの外周部より放出するシールレス構造の固体酸化物形燃料電池において、前記断熱ハウジングの内壁のうち、少なくとも天井面と周囲側面を、銀メッキ処理またはカロライズ処理を施した酸化スケール飛散防止板で覆うと共に、前記架台に銀メッキ処理またはカロライズ処理を施したことを特徴としている。
請求項２の発明は、請求項１に記載の固体酸化物形燃料電池であって、前記燃料電池スタックが、前記断熱ハウジング内に、高さ方向に複数、同一平面内に複数配設されていることを特徴としている。 The solid oxide fuel cell according to the first aspect of the present invention supports a fuel cell stack formed by stacking a large number of power generation cells by placing the fuel cell stack on a metal mount, and in a heat insulating housing having a metal inner wall. A sealless structure for storing and generating a power generation reaction by supplying a reaction gas to the inside of the fuel cell stack during operation and discharging the remaining gas not used in the power generation reaction from the outer periphery of the power generation cell In the solid oxide fuel cell, at least a ceiling surface and a peripheral side surface of the inner wall of the heat insulating housing are covered with an oxide scale scattering prevention plate subjected to silver plating treatment or calorization treatment, and the pedestal is subjected to silver plating treatment or It is characterized by having been calorized.
A second aspect of the present invention is the solid oxide fuel cell according to the first aspect, wherein a plurality of the fuel cell stacks are arranged in the heat insulating housing in the height direction and in the same plane. It is characterized by being.

請求項１の発明によれば、断熱ハウジングの内壁のうち少なくとも天井面と周囲側面を酸化スケール飛散防止板で覆ったので、断熱ハウジングの内壁から発生した酸化スケールを、燃料電池スタックの近傍へ飛散しないように規制することができる。また、燃料電池スタックを支持する架台に銀メッキ処理またはカロライズ処理を施したので、架台から酸化スケールが発生しないように規制することができる。従って、酸化スケールの燃料電池スタック周辺への浮遊や堆積を減らすことができ、酸化スケールが原因の短絡や地絡を防ぐことができる。   According to the invention of claim 1, since at least the ceiling surface and the peripheral side surface of the inner wall of the heat insulating housing are covered with the oxide scale scattering prevention plate, the oxide scale generated from the inner wall of the heat insulating housing is scattered near the fuel cell stack. It can be regulated not to. Further, since the gantry supporting the fuel cell stack is subjected to the silver plating process or the calorizing process, it is possible to regulate the oxide scale from being generated from the gantry. Therefore, floating and accumulation of oxide scale around the fuel cell stack can be reduced, and short circuit and ground fault caused by the oxide scale can be prevented.

請求項２の発明によれば、断熱ハウジング内に、高さ方向に複数、同一平面内に複数配設されている場合にも、酸化スケールの燃料電池スタック周辺への浮遊や堆積を減らすことができ、酸化スケールが原因の短絡や地絡を防ぐことができる。   According to the invention of claim 2, even when a plurality of the heat insulating housings are arranged in the height direction and in the same plane, the floating and accumulation of the oxide scale around the fuel cell stack can be reduced. It is possible to prevent a short circuit and a ground fault caused by the oxide scale.

以下、本発明の実施形態を説明する。
図１は実施形態の固体酸化物形燃料電池の概略構成を示す側断面図、図２は断熱ハウジングを構成する内部缶体に酸化スケール飛散防止板を張り付ける部位を示すための概略斜視図である。 Embodiments of the present invention will be described below.
FIG. 1 is a side sectional view showing a schematic configuration of a solid oxide fuel cell of an embodiment, and FIG. 2 is a schematic perspective view for showing a portion where an oxide scale scattering prevention plate is attached to an internal can body constituting a heat insulating housing. is there.

この固体酸化物形燃料電池１は、図３に示したものと燃料電池スタック３の段数が違うだけで、基本的な構成要素をほぼ同じくしたものであり、同等要素部分には同一符号を付して説明を省略する。   This solid oxide fuel cell 1 is similar to that shown in FIG. 3 except that the number of stages of the fuel cell stack 3 is different, and the basic components are substantially the same. Therefore, the description is omitted.

この固体酸化物形燃料電池１も、シールレスタイプの燃料電池スタック３を有するものであり、断熱ハウジング２内に、高さ方向および同一平面方向に複数の燃料電池スタック３を、ステンレス製の架台４１に支持を取りながら収容している。また、断熱ハウジング２は、ステンレス製の内部缶体２Ａを有するもので、その内部缶体２Ａの中に、架台４１や燃料電池スタック３、燃料ガス熱交換器３３、酸化剤ガス熱交換器３４等を収容している。これら熱交換器３３、３４を始めとして、金属製の部分である架台４１の表面には、銀メッキ処理やカロライズ処理が施されている。   This solid oxide fuel cell 1 also has a sealless type fuel cell stack 3, and a plurality of fuel cell stacks 3 are installed in a heat insulating housing 2 in the height direction and the same plane direction, and are made of stainless steel. 41 is accommodated while being supported. The heat insulating housing 2 has a stainless steel inner can body 2A, and the base 41, the fuel cell stack 3, the fuel gas heat exchanger 33, and the oxidant gas heat exchanger 34 are included in the inner can body 2A. Etc. are accommodated. Starting with these heat exchangers 33 and 34, the surface of the gantry 41, which is a metal part, is subjected to silver plating or calorizing.

カロライズ処理とは、アルミニウムを高温に加熱して素材表面に拡散させるものであり、カロライズ処理を施すことにより、ステンレス素材の中にアルミニウムが浸透し、表面がアルミニウム合金化する。   In the calorizing treatment, aluminum is heated to a high temperature and diffused on the surface of the material. By performing the calorizing treatment, the aluminum penetrates into the stainless steel material and the surface becomes an aluminum alloy.

また、大面積を有する内部缶体２Ａの内面（内壁）には、カロライズ処理を後から施すのは難しいので、図２に示すように、内面のうちの、底面２Ａ−３を除く、少なくとも天井面２Ａ−１と周囲側面２Ａ−２を、銀メッキ処理またはカロライズ処理を施した酸化スケール飛散防止板５０で覆っている。   Further, since it is difficult to perform calorizing treatment on the inner surface (inner wall) of the inner can body 2A having a large area, at least the ceiling excluding the bottom surface 2A-3 of the inner surface as shown in FIG. The surface 2A-1 and the surrounding side surface 2A-2 are covered with an oxide scale scattering prevention plate 50 that has been subjected to silver plating or calorizing.

このように、断熱ハウジング２の内部缶体２Ａの内面のうち少なくとも天井面２Ａ−１と周囲側面２Ａ−２を酸化スケール飛散防止板５０で覆った場合、内部缶体２Ａの内面から発生した酸化スケールを、燃料電池スタック３の近傍へ飛散しないように規制することができる。また、燃料電池スタック３を支持する架台４１にも、銀メッキ処理またはカロライズ処理を施しているので、架台４１から酸化スケールが発生しないように規制することができる。従って、酸化スケールの燃料電池スタック３周辺への浮遊や堆積を大幅に減らすことができ、酸化スケールが原因の短絡や地絡を未然に防ぐことができ、安定した運転が可能になる。   Thus, when at least the ceiling surface 2A-1 and the surrounding side surface 2A-2 of the inner surface of the inner can body 2A of the heat insulating housing 2 are covered with the oxide scale scattering prevention plate 50, the oxidation generated from the inner surface of the inner can body 2A. The scale can be regulated so as not to be scattered near the fuel cell stack 3. Further, since the gantry 41 that supports the fuel cell stack 3 is also subjected to the silver plating process or the calorizing process, it can be regulated so that no oxide scale is generated from the gantry 41. Therefore, floating and accumulation of oxide scale around the fuel cell stack 3 can be greatly reduced, and short circuit and ground fault caused by the oxide scale can be prevented in advance, and stable operation becomes possible.

本発明の実施形態の固体酸化物形燃料電池の概略構成を示す側断面図。1 is a side sectional view showing a schematic configuration of a solid oxide fuel cell according to an embodiment of the present invention. 断熱ハウジングを構成する内部缶体に酸化スケール飛散防止板を張り付ける部位を示すための概略斜視図。The schematic perspective view for showing the site | part which sticks an oxide scale scattering prevention board to the internal can which comprises a heat insulation housing. 従来の固体酸化物形燃料電池の例を示す縦断面図。The longitudinal cross-sectional view which shows the example of the conventional solid oxide fuel cell. 燃料電池スタックの要部構成図で、運転時のガスの流れを示す図。The figure which shows the gas flow at the time of a driving | operation in the principal part block diagram of a fuel cell stack.

符号の説明Explanation of symbols

１ 固体酸化物形燃料電池
２ 断熱ハウジング
２Ａ 内部缶体（断熱ハウジングの内壁）
３ 燃料電池スタック
４１ 架台
５０ 酸化スケール飛散防止板 1 Solid Oxide Fuel Cell 2 Heat Insulating Housing 2A Inner Can (Inner Wall of Heat Insulating Housing)
3 Fuel Cell Stack 41 Base 50 Oxide Scale Scatter Prevention Plate

Claims (2)

発電セルを多数積層して構成した燃料電池スタックを、金属製の架台に載せることで支持して、金属製の内壁を有する断熱ハウジング内に収納し、運転時に、前記燃料電池スタックの内部に反応用ガスを供給して発電反応を生じさせると共に、発電反応に使用されなかった残余のガスを、発電セルの外周部より放出するシールレス構造の固体酸化物形燃料電池において、
前記断熱ハウジングの内壁のうち、少なくとも天井面と周囲側面を、銀メッキ処理またはカロライズ処理を施した酸化スケール飛散防止板で覆うと共に、前記架台に銀メッキ処理またはカロライズ処理を施したことを特徴とする固体酸化物形燃料電池。 A fuel cell stack configured by stacking a large number of power generation cells is supported by placing it on a metal base, and is housed in a heat insulating housing having a metal inner wall, and reacts inside the fuel cell stack during operation. In a solid oxide fuel cell having a sealless structure in which a working gas is supplied to cause a power generation reaction and the remaining gas that has not been used in the power generation reaction is discharged from the outer periphery of the power generation cell.
Of the inner wall of the heat insulating housing, at least the ceiling surface and the surrounding side surface are covered with an oxidized scale scattering prevention plate subjected to silver plating treatment or calorizing treatment, and the gantry is subjected to silver plating treatment or calorizing treatment. Solid oxide fuel cell. 前記燃料電池スタックが、前記断熱ハウジング内に、高さ方向に複数、同一平面内に複数配設されていることを特徴とする請求項１に記載の固体酸化物形燃料電池。   2. The solid oxide fuel cell according to claim 1, wherein a plurality of fuel cell stacks are arranged in the heat insulation housing in the height direction and in the same plane.
JP2008089626A 2008-03-31 2008-03-31 Solid oxide fuel cell Expired - Fee Related JP5262241B2 (en)

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