JP4720185B2 - Membrane electrode composite for tubular fuel cell with heat insulation tube - Google Patents
Membrane electrode composite for tubular fuel cell with heat insulation tube Download PDFInfo
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- JP4720185B2 JP4720185B2 JP2005002506A JP2005002506A JP4720185B2 JP 4720185 B2 JP4720185 B2 JP 4720185B2 JP 2005002506 A JP2005002506 A JP 2005002506A JP 2005002506 A JP2005002506 A JP 2005002506A JP 4720185 B2 JP4720185 B2 JP 4720185B2
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本発明は、チューブ型燃料電池に用いられるチューブ形状の膜電極複合体が断熱管により覆われ、保温性が向上された断熱管付きチューブ型燃料電池用膜電極複合体に関する。 The present invention relates to a membrane electrode assembly for a tube-type fuel cell with a heat insulating tube in which a tube-shaped membrane electrode assembly used in a tube-type fuel cell is covered with a heat insulating tube to improve heat retention.
従来の平板構造の固体高分子電解質型燃料電池（以下、単に燃料電池と称する場合がある。）の最小発電単位である単位セルは、一般に固体電解質膜の両側に触媒電極層が接合されている膜電極複合体を有し、この膜電極複合体の両側にはガス拡散層が配されている。さらに、その外側にはガス流路を備えたセパレータが配されており、ガス拡散層を介して膜電極複合体の触媒電極層へと供給される燃料ガスおよび酸化剤ガスを通流させるとともに、発電により得られた電流を外部に伝える働きをしている。 A unit cell, which is a minimum power generation unit of a conventional solid polymer electrolyte fuel cell having a flat plate structure (hereinafter sometimes simply referred to as a fuel cell), generally has a catalyst electrode layer bonded to both sides of the solid electrolyte membrane. A membrane electrode assembly is provided, and gas diffusion layers are disposed on both sides of the membrane electrode assembly. Furthermore, a separator having a gas flow path is arranged outside thereof, and the fuel gas and the oxidant gas supplied to the catalyst electrode layer of the membrane electrode composite are passed through the gas diffusion layer, It works to transmit the current obtained by power generation to the outside.
上記燃料電池の小型化のため、および、単位体積当たりの発電反応面積を大きくするためには、燃料電池の上記構成部材の厚さを薄くする必要がある。しかしながら、このような従来の平板構造の燃料電池においては、各構成部材の厚さをある一定以下の値にすることは、機能面や強度面から好ましくなく、設計限界に近づきつつある。例えば、現在汎用されているナフィオン（商品名：Nafion、デュポン株式会社製）の膜は厚さが一定以下になるとガス透過性が大きくなりすぎ、セル内でガスのクロスリークが生じて発電電圧が低下する等の問題がある。このようなことから、従来の平板構造の燃料電池の単位体積当たりの出力密度を一定以上に向上させることは構造上困難である。 In order to reduce the size of the fuel cell and increase the power generation reaction area per unit volume, it is necessary to reduce the thickness of the constituent members of the fuel cell. However, in such a conventional flat-plate structure fuel cell, it is not preferable in terms of function and strength to make the thickness of each component member a certain value or less, and the design limit is approaching. For example, the membrane of Nafion (trade name: Nafion, manufactured by DuPont Co., Ltd.), which is widely used at present, becomes too gas permeable when its thickness is below a certain level, causing gas cross-leakage in the cell and generating voltage. There are problems such as lowering. For this reason, it is structurally difficult to improve the power density per unit volume of a conventional flat plate fuel cell to a certain level or more.
そこで、中空糸等を用い、その内面および外面に電解質膜や触媒電極層等を積層したチューブ形状の膜電極複合体を用いて燃料電池を構成することにより出力密度を高める研究が行なわれている。このようなチューブ形状の膜電極複合体は放熱性が高く、燃料電池システム内に熱がこもり難いため、従来の平板構造の燃料電池システムに用いられてきたような冷却装置を設ける必要がない。 Therefore, research has been conducted to increase the power density by constructing a fuel cell using a tubular membrane electrode assembly in which hollow fibers or the like are used and an electrolyte membrane, a catalyst electrode layer, etc. are laminated on the inner and outer surfaces thereof. . Such a tube-shaped membrane electrode assembly has a high heat dissipation property, and it is difficult for heat to be accumulated in the fuel cell system, so that it is not necessary to provide a cooling device as used in a conventional fuel cell system having a flat plate structure.
しかしながら、上述したようなチューブ型燃料電池においては、発電反応により生じる熱がすぐに放熱され、システム内の温度が上昇しないことに起因する不具合が発生する場合がある。例えば、低温雰囲気下で燃料電池を始動した場合は、生成水が凍結してガス流路を塞いでしまうことがあり、始動直後に膜電極複合体にガスを供給できなくなって運転が停止してしまう場合がある。 However, in the tube type fuel cell as described above, the heat generated by the power generation reaction is immediately radiated and there may be a problem caused by the temperature in the system not rising. For example, when the fuel cell is started in a low-temperature atmosphere, the generated water may freeze and block the gas flow path. Immediately after starting, the gas cannot be supplied to the membrane electrode assembly and the operation stops. May end up.
上記チューブ形状の膜電極複合体の例としては、例えば特許文献１に開示されている中空糸型固体高分子型燃料電池セルを挙げることができる。しかしながら、上記特許文献１においては、チューブ形状の膜電極複合体の放熱性については一切述べられておらず、低温雰囲気下での運転についても言及していない。
Examples of the tube-shaped membrane electrode assembly include a hollow fiber type solid polymer fuel cell disclosed in
本発明は上記問題点に鑑みてなされたものであり、保温性が高く、低温雰囲気下での運転に適した断熱管付きチューブ型燃料電池用膜電極複合体を提供することを主目的とするものである。 The present invention has been made in view of the above problems, and has as its main object to provide a membrane electrode assembly for a tube-type fuel cell with a heat insulating tube that has high heat retention and is suitable for operation in a low temperature atmosphere. Is.
上記目的を達成するために、本発明は、チューブ状の固体電解質膜と、上記固体電解質膜の外周面に形成された外側触媒電極層と、上記固体電解質膜の内周面に形成された内側触媒電極層と、上記外側触媒電極層の外周面に配置された外側集電体と、上記内側触媒電極層の内周面に配置された内側集電体とを少なくとも有するチューブ型燃料電池用膜電極複合体が、１本または複数本単位で断熱管に覆われていることを特徴とする断熱管付きチューブ型燃料電池用膜電極複合体を提供する。 To achieve the above object, the present invention provides a tubular solid electrolyte membrane, an outer catalyst electrode layer formed on the outer peripheral surface of the solid electrolyte membrane, and an inner surface formed on the inner peripheral surface of the solid electrolyte membrane. A tubular fuel cell membrane having at least a catalyst electrode layer, an outer current collector disposed on the outer peripheral surface of the outer catalyst electrode layer, and an inner current collector disposed on the inner peripheral surface of the inner catalyst electrode layer Provided is a membrane electrode assembly for a tubular fuel cell with a heat insulating tube, wherein the electrode composite is covered with a heat insulating tube in units of one or more.
本発明の断熱管付きチューブ型燃料電池用膜電極複合体（以下、チューブ型燃料電池用膜電極複合体を単に膜電極複合体と称する場合がある。）における膜電極複合体は、断熱管により覆われているため保温性が高く、発電反応により発生した熱を膜電極複合体内に留めておくことができる。そのため、低温雰囲気下で燃料電池を始動した場合でも、発電反応により発生した熱により膜電極複合体内の温度が急速に上昇するので、生成水が凍結してガス流路を塞ぐ等の不具合を防止することができ、円滑に始動することができる。 The membrane electrode assembly in the tubular fuel cell membrane electrode assembly with a heat insulating tube of the present invention (hereinafter, the membrane electrode assembly for a tubular fuel cell may be simply referred to as a membrane electrode assembly) is formed by a heat insulating tube. Since it is covered, heat retention is high, and heat generated by the power generation reaction can be retained in the membrane electrode assembly. Therefore, even when the fuel cell is started in a low-temperature atmosphere, the temperature inside the membrane electrode assembly rises rapidly due to the heat generated by the power generation reaction, preventing problems such as freezing of the generated water and blocking the gas flow path. Can be started smoothly.
上記本発明の断熱管付き膜電極複合体は、固体高分子型燃料電池に用いられることが好ましい。固体高分子型燃料電池は、固体電解質型やリン酸型などの他のタイプの燃料電池に比べて運転温度が低いため、上述したような低温雰囲気下での不具合が発生しやすく、本発明の効果が発揮されやすいからである。 The membrane electrode assembly with a heat insulating tube of the present invention is preferably used for a polymer electrolyte fuel cell. Since the polymer electrolyte fuel cell has a lower operating temperature than other types of fuel cells such as a solid electrolyte type and a phosphoric acid type, the above-mentioned problems are likely to occur in a low temperature atmosphere. This is because the effect is easily exhibited.
また、本発明は、膜電極複合体が１本単位で断熱管に覆われている上記断熱管付きチューブ型燃料電池用膜電極複合体が、複数本用いられていることを特徴とする断熱管付きチューブ型燃料電池（以下、チューブ型燃料電池を単に燃料電池と称する場合がある。）を提供する。１本単位で断熱管に覆われた断熱管付き膜電極複合体を用いて燃料電池を構成することにより、保温性が高く、かつ、温度分布が均一である燃料電池を得ることができる。 Further, the present invention provides a heat insulating tube characterized in that a plurality of the membrane electrode composites for a tubular fuel cell with a heat insulating tube, wherein the membrane electrode assembly is covered by a heat insulating tube in a unit of one, are used. Provided is a tube type fuel cell (hereinafter, the tube type fuel cell may be simply referred to as a fuel cell). By constituting a fuel cell using a membrane electrode assembly with a heat insulating tube covered by a heat insulating tube in a unit, a fuel cell having high heat retention and a uniform temperature distribution can be obtained.
本発明は、保温性が高く、低温雰囲気下での運転に適した断熱管付き膜電極複合体を得ることができるといった効果を奏する。 INDUSTRIAL APPLICABILITY The present invention has an effect that it is possible to obtain a membrane electrode assembly with a heat insulating tube that has high heat retention and is suitable for operation in a low temperature atmosphere.
本発明は、断熱管を有するチューブ型燃料電池用膜電極複合体、およびそれを用いたチューブ型燃料電池に関するものである。
以下、本発明の断熱管付きチューブ型燃料電池用膜電極複合体、および断熱管付きチューブ型燃料電池について、それぞれ説明する。
The present invention relates to a membrane electrode assembly for a tube type fuel cell having a heat insulating tube, and a tube type fuel cell using the same.
Hereinafter, the membrane electrode assembly for a tube type fuel cell with a heat insulating tube and the tube type fuel cell with a heat insulating tube of the present invention will be described.
Ａ．断熱管付きチューブ型燃料電池用膜電極複合体
以下、本発明の断熱管付きチューブ型燃料電池用膜電極複合体について詳細に説明する。
本発明の断熱管付き膜電極複合体は、断熱管で覆うことにより保温性が向上された膜電極複合体である。一般に燃料電池は、用いられている電解質材料の耐熱温度内において、より高い温度で運転した方が良好な発電特性を発揮する。本発明の断熱管付きチューブ型燃料電池用膜電極複合体は保温性が良好であり、発電反応により発生した熱を膜電極複合体内に留めることにより運転温度を高めることができるため、発電特性を向上させることが可能である。
A. Hereinafter, the membrane electrode assembly for a tube-type fuel cell with a heat insulating tube of the present invention will be described in detail.
The membrane electrode composite with a heat insulating tube of the present invention is a membrane electrode composite whose heat retention is improved by covering with a heat insulating tube. In general, a fuel cell exhibits better power generation characteristics when operated at a higher temperature within the heat resistant temperature of the electrolyte material used. The membrane electrode assembly for a tube-type fuel cell with a heat insulating tube of the present invention has good heat retention, and the operating temperature can be increased by retaining the heat generated by the power generation reaction in the membrane electrode assembly. It is possible to improve.
まず、本発明の断熱管付き膜電極複合体の構造について図を用いて説明する。
図１は、本発明の断熱管付き膜電極複合体の一例を示す概略構造図である。図１に示すように、本発明の断熱管付き膜電極複合体１は、膜電極複合体２が、断熱管３により覆われている構成を有する。上記膜電極複合体２の外側面と断熱管３との間には、ガスや生成水が通流可能なガス通流空間４が設けられている。本発明においては、図１に示すように、ガス通流空間４（網掛け部）が設けられているため、保温性能が高く、かつ、発電反応に必要な燃料ガスや酸化剤ガス、または発電反応により生成した生成水を円滑に通流させることができる。
以下、本発明の断熱管付き膜電極複合体を構成する断熱管、および膜電極複合体についてそれぞれ説明する。
First, the structure of the membrane electrode assembly with a heat insulating tube of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic structural diagram showing an example of a membrane electrode assembly with a heat insulating tube of the present invention. As shown in FIG. 1, a
Hereinafter, the heat insulating tube and the membrane electrode composite constituting the membrane electrode composite with a heat insulating tube of the present invention will be described.
１．断熱管
上記断熱管の内径は、上記膜電極複合体を覆うことができるものであれば特に限定されるものではない。例えば、膜電極複合体が１本単位で、断面形状が円形の断熱管に覆われている場合は、上記膜電極複合体の外径と上記断熱管の内径との差が１０〜１００００μｍの範囲内、中でも５００〜２０００μｍの範囲内であることが好ましい。膜電極複合体の外径と断熱管の内径との差を上記のように設定することにより、膜電極複合体の外側にガス通流空間を確保することができ、発電反応に必要な燃料ガスや酸化剤ガス、または発電反応により生成した生成水を円滑に通流させることができる。
1. Heat insulation tube The inner diameter of the heat insulation tube is not particularly limited as long as it can cover the membrane electrode assembly. For example, when the membrane electrode assembly is a single unit and is covered with a heat insulating tube having a circular cross-sectional shape, the difference between the outer diameter of the membrane electrode composite and the inner diameter of the heat insulating tube is in the range of 10 to 10,000 μm. Among these, it is preferable to be in the range of 500 to 2000 μm. By setting the difference between the outer diameter of the membrane electrode assembly and the inner diameter of the heat insulating tube as described above, a gas flow space can be secured outside the membrane electrode assembly, and the fuel gas necessary for the power generation reaction In addition, it is possible to smoothly flow oxidant gas or generated water generated by the power generation reaction.
上述したような断熱管の厚さは、用いられる材料により大きく異なるものではあるが、１００μｍ〜１００００μｍの範囲内、中でも１０００μｍ〜２０００μｍの範囲内であることが好ましい。断熱管の厚さが上記範囲に満たないと、保温機能が十分でない可能性がある。一方、厚さが上記範囲を超えると、断熱管付き膜電極複合体が大型化してしまい、単位体積当たりの出力密度が低下してしまう可能性がある。 The thickness of the heat insulating tube as described above varies greatly depending on the material used, but is preferably in the range of 100 μm to 10000 μm, and more preferably in the range of 1000 μm to 2000 μm. If the thickness of the heat insulating tube is less than the above range, the heat retaining function may not be sufficient. On the other hand, when the thickness exceeds the above range, the membrane electrode assembly with a heat insulating tube may be enlarged, and the output density per unit volume may be reduced.
本発明において断熱管を形成する材料は、熱伝導性が低いものであれば特に限定されるものではなく、例えば、セラミックス（アルミナ、ジルコニア、シリカ、ゼオライト）等を用いることができる。中でもアルミナ等の無機系の材料が好適に用いられる。 In the present invention, the material for forming the heat insulating tube is not particularly limited as long as it has low thermal conductivity. For example, ceramics (alumina, zirconia, silica, zeolite) or the like can be used. Of these, inorganic materials such as alumina are preferably used.
なお、本発明において膜電極複合体を覆う断熱管の形状は、１本または複数本の膜電極複合体を覆うことができる形状であれば特に限定されるものではないが、通常は図２（ａ）に例示するように、膜電極複合体が１本単位で、断面形状が円形状の断熱管に覆われている。また、複数の膜電極複合体が１つの断熱管により覆われていてもよく、例えば図２（ｂ）および図２（ｃ）に例示するような、楕円形、矩形などのような断面形状を有する管形状のもの等も用いることができる。この際、断熱管の断面形状は、その内側に配される膜電極複合体の形に合わせて、その一部に凹凸があるような形状であってもよい。 In the present invention, the shape of the heat insulating tube that covers the membrane electrode assembly is not particularly limited as long as it is a shape that can cover one or a plurality of membrane electrode assemblies. As illustrated in a), a membrane electrode assembly is covered by a heat insulating tube having a single unit and a circular cross section. In addition, a plurality of membrane electrode assemblies may be covered with a single heat insulating tube, and have a cross-sectional shape such as an ellipse or a rectangle as exemplified in FIG. 2 (b) and FIG. 2 (c). The thing of the tube shape which has can also be used. Under the present circumstances, the cross-sectional shape of a heat insulation pipe | tube may be a shape which has an unevenness | corrugation in the part according to the shape of the membrane electrode complex distribute | arranged to the inner side.
２．膜電極複合体
本発明の断熱管付き膜電極複合体において、断熱管の内側に配される膜電極複合体は特に限定されるものではなく、一般的なチューブ形状の膜電極複合体を用いることができる。一般的なチューブ形状の膜電極複合体の構成としては、例えば、内側集電体、その外側面上に内側触媒電極層、固体電解質膜、外側触媒電極層、および外側集電体がこの順に積層されているもの等を挙げることができる。
以下、本発明に用いられる膜電極複合体の各構成について説明する。
2. Membrane electrode composite In the membrane electrode composite with a heat insulating tube of the present invention, the membrane electrode composite disposed inside the heat insulating tube is not particularly limited, and a general tube-shaped membrane electrode composite is used. Can do. As a configuration of a general tube-shaped membrane electrode composite, for example, an inner current collector, an inner catalyst electrode layer, a solid electrolyte membrane, an outer catalyst electrode layer, and an outer current collector are laminated in this order on the outer surface. Can be mentioned.
Hereinafter, each structure of the membrane electrode assembly used in the present invention will be described.
本発明に用いられる固体電解質膜としては、チューブ状の形態を有し、プロトン伝導性に優れ、かつ電流を流さない材料からなるものであれば特に限定されるものではない。このような固体電解質膜を形成する電解質材料としては、ナフィオン（商品名：Nafion、デュポン株式会社製）などに代表されるようなフッ素系樹脂、アミド系樹脂に代表されるような炭化水素系樹脂等有機系のもの、または、ケイ素酸化物を主成分とするものなどの無機系のもの等を挙げることができ、中でも炭化水素系樹脂や無機系のもの、特に無機系のものが好ましい。炭化水素系樹脂や無機系の電解質材料は耐熱性が高く、高い温度での運転が可能であるからである。本発明においては、運転中に発生した熱を膜電極複合体内に留めることができ、高い温度での運転が可能であるため、高い耐熱性を有する電解質材料を用いることにより、膜電極複合体の発電特性をさらに向上することができる。 The solid electrolyte membrane used in the present invention is not particularly limited as long as it has a tubular form, is excellent in proton conductivity, and is made of a material that does not flow current. Examples of the electrolyte material for forming such a solid electrolyte membrane include fluorine resins such as Nafion (trade name: Nafion, manufactured by DuPont) and hydrocarbon resins such as amide resins. Examples thereof include organic materials such as inorganic materials such as those mainly composed of silicon oxide, and hydrocarbon resins and inorganic materials, particularly inorganic materials are preferred. This is because hydrocarbon resins and inorganic electrolyte materials have high heat resistance and can be operated at high temperatures. In the present invention, heat generated during operation can be retained in the membrane electrode assembly, and operation at a high temperature is possible. Therefore, by using an electrolyte material having high heat resistance, the membrane electrode assembly The power generation characteristics can be further improved.
上記無機系の電解質材料を用いた固体電解質膜としては、多孔質ガラスをチューブ状に成形し、そのナノ細孔内の表面を改質して、プロトン導電性を付与したチューブ状固体電解質膜や、チューブ状のリン酸ガラスを応用したもの等を挙げることができる。上記多孔質ガラスを用いたものとしては、例えば多孔質ガラスの細孔内表面のＯＨ基にメルカプトプロピルトリメトキシシランのシランカップリング剤を反応させ、その後にメルカプト基の−ＳＨを酸化することにより、プロトン伝導性を有するスルホン酸基を導入する方法（化学と工業 第５７巻 第１号(２００４年）ｐ４１〜ｐ４４）等を挙げることができる。また、リン酸ガラスを応用したものとしては、燃料電池 Ｖｏｌ．３ Ｎｏ．３ ２００４ ｐ６９〜ｐ７１に報告された例等を挙げることができる。 As the solid electrolyte membrane using the inorganic electrolyte material, a tube-shaped solid electrolyte membrane provided with proton conductivity by forming a porous glass into a tube shape, modifying the surface in the nanopore, In addition, a tube-like phosphate glass is applied. As the above-mentioned porous glass, for example, by reacting a silane coupling agent of mercaptopropyltrimethoxysilane with an OH group on the pore inner surface of the porous glass, and then oxidizing -SH of the mercapto group. And a method of introducing a sulfonic acid group having proton conductivity (Chemical and Industrial Vol. 57 No. 1 (2004) p41 to p44). In addition, as an application of phosphate glass, fuel cell Vol. 3 No. 3 2004 p69 to p71 can be mentioned.
また、本発明に用いられる内側触媒電極層、および外側触媒電極層は特に限定されるものではなく、通常の平面構造の燃料電池用膜電極複合体に用いられている材料をチューブ形状に成形したものを用いることが可能である。具体的には、パーフルオロスルホン酸系ポリマー（商品名：NafionTM、デュポン株式会社製）等のプロトン伝導材、カーボンブラックやカーボンナノチューブ等の導電性材料、および上記導電性材料に担持された白金等の触媒を含むものである。 Further, the inner catalyst electrode layer and the outer catalyst electrode layer used in the present invention are not particularly limited, and a material used for a fuel cell membrane electrode composite having a normal planar structure is formed into a tube shape. Can be used. Specifically, proton conductive materials such as perfluorosulfonic acid polymer (trade name: Nafion ™ , manufactured by DuPont), conductive materials such as carbon black and carbon nanotubes, and platinum supported on the conductive material And the like.
本発明に用いられる膜電極複合体において、発電反応により発生した電力の集電方法は特に限定されるものではなく、通常のチューブ形状の膜電極複合体における集電の方法により行うことができる。例えば、触媒電極層としての機能と、集電体としての機能とを併せ持つ部材を、上記内側触媒電極層および内側集電体、または外側触媒電極層および外側集電体として用いてもよい。また、触媒電極層とは別の部材を集電体として用い、上記内側触媒電極層の内側に内側集電体、または上記外側触媒電極層の外側に外側集電体を形成してもよい。本発明においては、触媒電極層に導電性の高い集電体を密着させて集電を行うことにより、電子の移動を円滑にし、効率よく集電を行うことができることから、触媒電極層とは別の部材である集電体を用いて集電を行うことが好ましい。 In the membrane electrode assembly used in the present invention, the method for collecting the electric power generated by the power generation reaction is not particularly limited, and can be performed by the method for collecting current in a normal tube-shaped membrane electrode assembly. For example, a member having both a function as a catalyst electrode layer and a function as a current collector may be used as the inner catalyst electrode layer and the inner current collector, or the outer catalyst electrode layer and the outer current collector. Further, a member different from the catalyst electrode layer may be used as a current collector, and an inner current collector may be formed inside the inner catalyst electrode layer, or an outer current collector may be formed outside the outer catalyst electrode layer. In the present invention, by collecting current by bringing a highly conductive current collector into close contact with the catalyst electrode layer, it is possible to smoothly move electrons and to collect current efficiently. It is preferable to collect current using a current collector which is another member.
上記内側集電体、および外側集電体は導電性が高く、膜電極複合体のチューブ形状の径方向にガスを透過するものであれば特に限定されるものではない。このような内側集電体、および外側集電体の形状の例としては、バネ形状のもの、管の壁面部に、その壁面を貫通する孔を多数有する形状や、管の壁面部が網目構造のもの、複数の直線状の導電体がチューブ形状の軸方向に配置されたもの等を挙げることができ、中でもバネ形状のものが好適に用いられる。また、このような形状の内側集電体、および外側集電体を形成する材料としては、例えば、カーボンまたは、ステンレス鋼、チタン、白金、金、ＴｉＣ、ＴｉＳｉ２、ＳｉＯ２，Ｂ２Ｏ３，Ｎｄ２Ｏ，ＴｉＢ２等の金属等を挙げることができる。
The inner current collector and the outer current collector are not particularly limited as long as they have high conductivity and allow gas to permeate in the radial direction of the tube shape of the membrane electrode assembly. Examples of the shape of the inner current collector and the outer current collector include a spring shape, a shape having a large number of holes penetrating the wall surface of the tube, and a wall surface of the tube having a mesh structure. And those in which a plurality of linear conductors are arranged in the axial direction of a tube shape. Among them, a spring shape is preferably used. The inner current collector having such a shape, and as a material for forming the outer collector, for example, carbon or stainless steel, titanium, platinum, gold, TiC, TiSi 2, SiO 2 , B 2
３．断熱管付き膜電極複合体
本発明の断熱管付き膜電極複合体は、上記膜電極複合体が１本または複数本単位において上記断熱管により覆われているものである。このような断熱管付き膜電極複合体においては、内側触媒電極層および外側触媒電極層のうち、どちらが空気極、燃料極でもよいが、内側触媒電極層が空気極であり、外側触媒電極層が燃料極であることが好ましい。膜電極複合体において生成水が発生するのは空気極側であるため、空気極を外気から離れた、膜電極複合体の内側に配置することにより、低温雰囲気下での運転中の生成水の凍結をより効果的に防止することができるからである。また、膜電極複合体においては、空気極側で熱が発生するため、熱の発生源を外気から離れた膜電極複合体の内側に配置することにより、保温性も向上させることができる。
3. Membrane electrode composite with a heat insulating tube The membrane electrode composite with a heat insulating tube of the present invention is one in which the membrane electrode composite is covered with the heat insulating tube in one or more units. In such a membrane electrode assembly with a heat insulating tube, either the inner catalyst electrode layer or the outer catalyst electrode layer may be an air electrode or a fuel electrode, but the inner catalyst electrode layer is an air electrode, and the outer catalyst electrode layer is A fuel electrode is preferred. Since the generated water is generated on the air electrode side in the membrane electrode assembly, the generated water during operation in a low-temperature atmosphere can be obtained by disposing the air electrode inside the membrane electrode assembly away from the outside air. This is because freezing can be more effectively prevented. In addition, since heat is generated on the air electrode side in the membrane electrode assembly, the heat retention can be improved by arranging the heat generation source inside the membrane electrode assembly away from the outside air.
本発明において、１つの断熱管により覆われる膜電極複合体の本数は特に限定されるものではなく、チューブ形状の膜電極複合体が１本単位（図２（ａ）参照。）で上記断熱管に覆われていても、複数本単位（図２（ｂ）参照。）で覆われていてもよい。また、チューブ形状の膜電極複合体を多数含有する燃料電池全体が１単位（図２（ｃ）参照。）として断熱管に覆われていてもよい。本発明においては、上記の中でも、膜電極複合体が１〜１０本単位で断熱管に覆われていることが好ましく、特に膜電極複合体が１本単位で断熱管に覆われていることが好ましい。膜電極複合体を本数の少ない単位で覆った方が高い断熱効果が得られ、また、各膜電極複合体間の温度分布を均一にすることができるからである。 In the present invention, the number of membrane electrode composites covered by one heat insulating tube is not particularly limited, and the above-mentioned heat insulating tube is a unit of a tube-shaped membrane electrode composite (see FIG. 2A). Even if it is covered, it may be covered by a plurality of units (see FIG. 2B). Moreover, the whole fuel cell containing many tube-shaped membrane electrode composites may be covered with the heat insulation pipe | tube as 1 unit (refer FIG.2 (c)). In the present invention, among the above, the membrane electrode assembly is preferably covered with a heat insulating tube in units of 1 to 10, and in particular, the membrane electrode complex is covered with a heat insulating tube in units of one. preferable. This is because covering the membrane electrode assembly with a small number of units provides a higher heat insulation effect and makes it possible to make the temperature distribution between the membrane electrode assemblies uniform.
本発明においては、上述したような断熱管付き膜電極複合体が、固体高分子型燃料電池に用いられることが好ましい。固体高分子型の燃料電池は、固体電解質型やリン酸型などの他のタイプの燃料電池に比べて運転温度が低いため、低温雰囲気下で運転される場合がある。このような場合は、上述したように、生成水が凍結する等の不具合が発生する可能性があるが、本発明の断熱管付き膜電極複合体を用いることにより、このような不具合を防止することができる。 In the present invention, the membrane electrode assembly with a heat insulating tube as described above is preferably used for a polymer electrolyte fuel cell. A solid polymer fuel cell has a lower operating temperature than other types of fuel cells such as a solid electrolyte type and a phosphoric acid type, and may be operated in a low temperature atmosphere. In such a case, as described above, there is a possibility that a problem such as freezing of generated water may occur, but such a problem is prevented by using the membrane electrode assembly with a heat insulating tube of the present invention. be able to.
Ｂ．断熱管付きチューブ型燃料電池
次に、本発明の断熱管付きチューブ型燃料電池について説明する。
本発明の断熱管付きチューブ型燃料電池は、膜電極複合体が１本単位で断熱管に覆われている、上述した断熱管付きチューブ型燃料電池用膜電極複合体が、複数本用いられていることを特徴とするものである。このように、１本単位で断熱管に覆われた膜電極複合体を用いて断熱管付き燃料電池を構成することにより、発電反応により発生した熱を効果的に保温することができる。また、単セルである膜電極複合体を複数本用いて構成されたスタックを１単位として断熱管で覆った燃料電池の場合と比べ、本発明の燃料電池は膜電極複合体毎に断熱管で覆われているため、燃料電池内の温度分布が均一である。そのため、燃料電池内の全ての領域において良好な発電特性を発揮することができ、高い発電効率の燃料電池を得ることができる。
B. Next, a tube type fuel cell with a heat insulation tube of the present invention will be described.
The tube type fuel cell with a heat insulating tube of the present invention includes a plurality of the above-mentioned membrane electrode assemblies for a tube type fuel cell with a heat insulating tube, each of which is covered with a heat insulating tube. It is characterized by being. Thus, the heat generated by the power generation reaction can be effectively retained by configuring the fuel cell with the heat insulating tube using the membrane electrode assembly covered by the heat insulating tube in units of one. In addition, the fuel cell according to the present invention has a heat insulating tube for each membrane electrode composite as compared with a fuel cell in which a stack composed of a plurality of single cell membrane electrode composites is covered with a heat insulating tube as a unit. Since it is covered, the temperature distribution in the fuel cell is uniform. Therefore, good power generation characteristics can be exhibited in all regions in the fuel cell, and a fuel cell with high power generation efficiency can be obtained.
本発明の断熱管付き燃料電池の構成は、膜電極複合体が１本単位で断熱管に覆われているものであれば特に限定されるものではない。例えば、図３に示すように、複数の断熱管付き膜電極複合体が、密に配された構成を挙げることができる。このような燃料電池を構成する断熱管付き膜電極複合体は、図１や図２（ａ）に示す断熱管付き膜電極複合体と同様な構成を有するものである。本発明の断熱管付き燃料電池に用いられる断熱管付き膜電極複合体については、上記「Ａ．断熱管付きチューブ型燃料電池用膜電極複合体」と同様であるので、ここでの説明は省略する。 The configuration of the fuel cell with a heat insulating tube of the present invention is not particularly limited as long as the membrane electrode assembly is covered by the heat insulating tube in units of one. For example, as shown in FIG. 3, a configuration in which a plurality of membrane electrode composites with heat insulating tubes are densely arranged can be mentioned. The membrane electrode assembly with a heat insulating tube constituting such a fuel cell has the same configuration as the membrane electrode assembly with a heat insulating tube shown in FIG. 1 and FIG. The membrane electrode assembly with a heat insulation tube used in the fuel cell with a heat insulation tube of the present invention is the same as the above-mentioned “A. Membrane electrode assembly for a tube type fuel cell with a heat insulation tube”, and the description thereof is omitted here. To do.
また、本発明の断熱管付き燃料電池は、固体高分子型燃料電池であることが好ましい。上述した断熱管付き膜電極複合体の場合と同様に、本発明の断熱管付き燃料電池を固体高分子型燃料電池にすることにより、本発明の効果をより発揮することができるからである。 Moreover, it is preferable that the fuel cell with a heat insulating tube of the present invention is a solid polymer fuel cell. This is because, as in the case of the membrane electrode assembly with a heat insulating tube described above, the effect of the present invention can be further exhibited by making the fuel cell with a heat insulating tube of the present invention a solid polymer fuel cell.
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は、例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
例えば、上記説明においては、膜電極複合体は長手方向、および断面形状において全体が覆われているように説明されているが、本発明においてはこれらの態様に限定されず、膜電極複合体の長手方向の一部、または断面形状の一部が断熱管により覆われていない形状でもよい。本発明は、このような構成をも含むものである。
In addition, this invention is not limited to the said embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
For example, in the above description, the membrane electrode assembly is described as being entirely covered in the longitudinal direction and the cross-sectional shape. However, in the present invention, the membrane electrode assembly is not limited to these embodiments. A shape in which a part in the longitudinal direction or a part of the cross-sectional shape is not covered by the heat insulating tube may be used. The present invention includes such a configuration.
１ … 断熱管付き膜電極複合体
２ … 膜電極複合体
３ … 断熱管
４ … ガス通流空間
DESCRIPTION OF
Claims (3)
前記断熱管付きチューブ型燃料電池用膜電極複合体が、固体高分子型燃料電池に用いられ、
前記断熱管の材料が、セラミックスであることを特徴とする断熱管付きチューブ型燃料電池用膜電極複合体。 A tubular solid electrolyte membrane, an outer catalyst electrode layer formed on the outer peripheral surface of the solid electrolyte membrane, an inner catalyst electrode layer formed on the inner peripheral surface of the solid electrolyte membrane, and an outer periphery of the outer catalyst electrode layer A membrane fuel cell membrane electrode assembly having at least one outer current collector disposed on the surface and an inner current collector disposed on the inner peripheral surface of the inner catalyst electrode layer is one or more in units. a membrane electrode assembly for cross exchanger tube with tubular fuel cell covered by the heat-insulated pipe,
The membrane electrode assembly for a tubular fuel cell with a heat insulating tube is used for a solid polymer fuel cell,
2. A membrane electrode assembly for a tube type fuel cell with a heat insulating tube, wherein the material of the heat insulating tube is ceramics.
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|---|---|---|---|---|
| JPH08507896A (en) * | 1993-03-20 | 1996-08-20 | キール・ユニバーシティ | Solid oxide fuel cell structure |
| JPH09223507A (en) * | 1996-02-15 | 1997-08-26 | Matsushita Electric Ind Co Ltd | Solid polymer fuel cell |
| JPH1050331A (en) * | 1996-08-06 | 1998-02-20 | Fujikura Ltd | Solid electrolyte fuel cell and manufacture thereof |
| JP2002280041A (en) * | 2001-03-21 | 2002-09-27 | Toto Ltd | Fuel cell electric power generating system |
| JP2002539587A (en) * | 1999-03-06 | 2002-11-19 | フラウンホファー ゲセルシャフトツール フェールデルンク ダー アンゲヴァンテン フォルシュンク エー．ファオ． | Manufacture of tubular fuel cells, fuel cell modules, basic elements and ion exchange membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08507896A (en) * | 1993-03-20 | 1996-08-20 | キール・ユニバーシティ | Solid oxide fuel cell structure |
| JPH09223507A (en) * | 1996-02-15 | 1997-08-26 | Matsushita Electric Ind Co Ltd | Solid polymer fuel cell |
| JPH1050331A (en) * | 1996-08-06 | 1998-02-20 | Fujikura Ltd | Solid electrolyte fuel cell and manufacture thereof |
| JP2002539587A (en) * | 1999-03-06 | 2002-11-19 | フラウンホファー ゲセルシャフトツール フェールデルンク ダー アンゲヴァンテン フォルシュンク エー．ファオ． | Manufacture of tubular fuel cells, fuel cell modules, basic elements and ion exchange membranes |
| JP2002280041A (en) * | 2001-03-21 | 2002-09-27 | Toto Ltd | Fuel cell electric power generating system |
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