JP2011029150A - Reaction layer for fuel cell - Google Patents
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Abstract
Description
本発明は、燃料電池用反応層に関する。 The present invention relates to a reaction layer for a fuel cell.
燃料電池装置において従来では空気供給系に加湿器を配置し、プロセス空気の湿度を制御することにより、固体電解質膜及び反応層（以下、「膜電極接合体」ということがある）の水分状態を調整していた。しかしながら、昨今の燃料電池に要求される高効率化の観点から、燃料電池装置から加湿器等の補機が除去される傾向にある。その場合、燃料電池の運転環境に応じて膜電極接合体の水分状態を常に適正に維持できないおそれがある。
例えば、燃料電池を低加湿環境で運転すると、膜電極接合体は乾燥状態となってそのプロトン伝導性が低下し、充分な発電特性を発揮できなくなる。他方、燃料電池を高加湿環境で運転すると、いわゆるフラッディングが発生し発電特性の低下をきたす。
Conventionally, in a fuel cell device, a humidifier is disposed in an air supply system, and the moisture state of the solid electrolyte membrane and the reaction layer (hereinafter sometimes referred to as “membrane electrode assembly”) is controlled by controlling the humidity of the process air. I was adjusting. However, from the viewpoint of high efficiency required for recent fuel cells, auxiliary devices such as humidifiers tend to be removed from the fuel cell device. In that case, there is a possibility that the moisture state of the membrane electrode assembly cannot always be properly maintained according to the operating environment of the fuel cell.
For example, when the fuel cell is operated in a low humidified environment, the membrane electrode assembly becomes dry and its proton conductivity is lowered, so that sufficient power generation characteristics cannot be exhibited. On the other hand, when the fuel cell is operated in a highly humid environment, so-called flooding occurs and power generation characteristics deteriorate.
これらの現象を回避するため、反応層を二層構造とし、固体電解質膜側の第１の層を高保湿化し、他方、拡散層側の第２の層を低保湿化（高排水、高透気化）することが提案されている（特許文献１参照）。
これにより、低加湿環境化においても第1の層は湿潤状態に保たれ、高加湿環境下に滞留した水分が第２の層から効率よく排出される。
In order to avoid these phenomena, the reaction layer has a two-layer structure, the first layer on the solid electrolyte membrane side is highly moisturized, while the second layer on the diffusion layer side is low in moisture retention (high drainage, high permeability). It has been proposed to vaporize (see Patent Document 1).
As a result, even in a low humidified environment, the first layer is kept in a wet state, and the water staying in the highly humidified environment is efficiently discharged from the second layer.
しかしながら、上記の構成では第1の層と第２の層とが連続的に形成されているため、低加湿環境下において本来第1の層に保持されるべき水分が乾燥傾向にある第２の層へ拡散し、プロトン伝導性を低下させてしまうおそれがある。 However, in the above configuration, since the first layer and the second layer are continuously formed, the moisture that should originally be retained in the first layer in a low humidified environment tends to dry. There is a risk of diffusing into the layer and reducing proton conductivity.
上記課題を解決すべく本発明者らは鋭意研究検討を重ねた結果、高保湿の第1の層と低保湿の第２の層との間に触媒が担持されない中間層を介在させた。即ち、この発明の第１の局面は次のように規定される。
燃料電池において固体電解質膜と拡散層との間に介在される反応層であって、
前記固体電解質膜に接する第１の層と、前記拡散層に接する第２の層と、前記第１の層と前記第２の層との間に介在される中間層とを備え、前記第１の層と第２の層は、導電性の単体に担持された触媒を有し、かつ第１の層は前記第２の層より保湿性が高く、前記中間層には触媒が存在しない、ことを特徴とする燃料電池用反応層。
As a result of intensive studies and studies to solve the above problems, the present inventors intervened an intermediate layer in which no catalyst is supported between the first layer having high moisture retention and the second layer having low moisture retention. That is, the first aspect of the present invention is defined as follows.
A reaction layer interposed between a solid electrolyte membrane and a diffusion layer in a fuel cell,
A first layer in contact with the solid electrolyte membrane; a second layer in contact with the diffusion layer; and an intermediate layer interposed between the first layer and the second layer, The first layer and the second layer have a catalyst supported on a conductive simple substance, and the first layer has higher moisture retention than the second layer, and the intermediate layer has no catalyst. A reaction layer for a fuel cell.
このように規定される第１の局面の燃料電池反応層によれば、低加湿環境下で主に発電が起こる第１の層の生成水が、第２の層には拡散し難く、ガスによる持去りを抑制することができる。これは、中間層により第１の層と第２の層が物理的に隔てられ、拡散距離が増すためと考えられる。その結果、電解質膜と第１の層のみが湿潤状態に保たれ、低湿度環境でも高性能を発揮する。
他方、高加湿環境下では、過剰になった生成水が、中間層に拡散するため、第1の層におけるフラッディングの発生を防止できる。
According to the fuel cell reaction layer of the first aspect defined as described above, the generated water of the first layer in which power generation mainly occurs in a low humid environment is difficult to diffuse into the second layer, and is based on gas. Taking away can be suppressed. This is considered because the first layer and the second layer are physically separated by the intermediate layer, and the diffusion distance is increased. As a result, only the electrolyte membrane and the first layer are kept in a wet state, and high performance is exhibited even in a low humidity environment.
On the other hand, in a highly humid environment, excess generated water diffuses into the intermediate layer, so that flooding in the first layer can be prevented.
この発明の第２の局面は次のように規定される。即ち、第1の局面で規定される燃料電池用反応層において、前記中間層は前記第１の層より保湿性が低くかつ前記第２の層より保湿性が高い。
このように規定される第２の局面の反応層によれば、中間層がバッファ層としてより確実に機能する。
The second aspect of the present invention is defined as follows. That is, in the fuel cell reaction layer defined in the first aspect, the intermediate layer has lower moisture retention than the first layer and higher moisture retention than the second layer.
According to the reaction layer of the second aspect defined in this way, the intermediate layer functions more reliably as a buffer layer.
この発明の第３の局面は次のように規定される。即ち、第１の局面に規定の燃料電池用反応層において、前記中間層は前記第１の層に接する第３−１の層と、前記第２の層に接する第３‐２の層と、該第３−１の層と該第３−２の層とに挟まれる第３−３の層を備え、
前記第３−１の層は前記第１の層と同じか若しくはそれより低い保湿性でありかつ前記第３−２の層より高い保湿性を有し、前記第３−２の層は前記第２の層と同じかそれより高い保湿性を有し、前記第３−３の層は前記第３−１の層及び前記第３−２の層より高い保湿性を有する。
このように規定される中間層ではその中心となる層の保湿性を高くすることにより、燃料電池用反応層として優れた性能を奏するものとなる。例えば低加湿環境においては第１の層で生成された生成水が保湿性の高い第３−３の層で吸水（トラップ）され、この第３−３の層より外側（第３−２の層、第２の層、即ち拡散層側）の層への生成水の移動が防止される。これら外側の層は拡散層におけるガス流れの影響を受けやすいので、即ち生成水が持ち去られやすいので、この第３−３の層で生成水をトラップすることにより、低加湿環境下における第１の層の過乾燥を防止し、そこでの燃料電池反応の高い効率を確保する。
なお、第３の局面において、触媒を備えないことの他は前記第３−１の層を前記第１の層と同じ特性とし、同じく触媒を備えないことの他は前記第３−２の層を前記第２の層と同じ特性とすることが好ましい（第４の局面）。例えば、同一細孔径（第１の細孔径）を有するカーボン粒子で第３−１の層と第１の層とを構成し、同様に同一細孔径（第２の細孔径）を有するカーボン粒子で第３−２層と第２の層とを構成する。第３−１の層を構成するカーボン粒子の細孔径と第１の層を構成するカーボン粒子の細孔径とが異なる場合に比べて、細孔径が同一とされた両層間では水の移動がより円滑に行われる。第３−２の層と第２の層との間においてもその細孔径を同じくすることにより水の移動が円滑になり、もって、高加湿環境下におけるフラッディングの防止に役立つ。
The third aspect of the present invention is defined as follows. That is, in the fuel cell reaction layer defined in the first aspect, the intermediate layer includes a 3-1 layer in contact with the first layer, a 3-2 layer in contact with the second layer, A 3-3 layer sandwiched between the 3-1 layer and the 3-2 layer;
The 3-1 layer has the same or lower moisture retention as the first layer and has a higher moisture retention than the 3-2 layer, and the 3-2 layer is the first layer. The 3-3 layer has the same or higher moisture retention than the second layer, and the 3-3 layer has higher moisture retention than the 3-1 layer and the 3-2 layer.
In the intermediate layer defined in this way, by increasing the moisture retention of the central layer, the intermediate layer exhibits excellent performance as a fuel cell reaction layer. For example, in a low humidification environment, the generated water generated in the first layer is absorbed (trapped) by the 3-3 layer having high moisture retention, and outside the 3-3 layer (the 3-2 layer). The generated water is prevented from moving to the second layer (ie, the diffusion layer side). Since these outer layers are easily affected by the gas flow in the diffusion layer, that is, the generated water is easily taken away, trapping the generated water in the third to third layers allows the first layer under the low humid environment to be removed. Prevent over-drying of the layer and ensure high efficiency of the fuel cell reaction there.
In the third aspect, the 3-1 layer has the same characteristics as the first layer except that no catalyst is provided, and the 3-2 layer except that the catalyst is not provided. It is preferable to have the same characteristics as those of the second layer (fourth aspect). For example, the carbon particles having the same pore diameter (first pore diameter) constitute the 3-1 layer and the first layer, and similarly, the carbon particles having the same pore diameter (second pore diameter). The 3-2 layer and the second layer are configured. Compared with the case where the pore diameters of the carbon particles constituting the 3-1 layer and the pore diameters of the carbon particles constituting the first layer are different, the movement of water between the two layers having the same pore diameter is greater. It is done smoothly. By making the pore diameters the same between the 3-2 layer and the second layer, the water can move smoothly, which helps prevent flooding in a highly humid environment.
この発明の第５の局面は次のように規定される。即ち、第１〜第４のいずれかの局面に規定の燃料電池用反応層であって、前記第１の層は前記第２の層に比べて担体の空隙率が低く、電解質比率が大きく、触媒の担持密度が高く、若しくは該電解質のＥＷが低い。
かかる第５の局面は保湿性を調整する具体的方策を列挙したものであり、かかる方策を採用することにより、安価でかつ確実に各層の保湿性を制御可能となる。
The fifth aspect of the present invention is defined as follows. That is, the fuel cell reaction layer defined in any one of the first to fourth aspects, wherein the first layer has a lower carrier porosity and a higher electrolyte ratio than the second layer, The catalyst loading density is high, or the EW of the electrolyte is low.
The fifth aspect enumerates specific measures for adjusting the moisture retention, and by adopting such measures, the moisture retention of each layer can be reliably controlled at low cost.
この発明の実施形態の燃料電池１を図１に示す。
この燃料電池１は固体電解質膜２を水素極１０と空気極２０とで挟んだ構成である。
固体電解質膜２にはプロトン導電性の高分子材料、例えばナフィオン（デュポン社商標名、以下同じ）等のフッ素系ポリマーを用いることができる。
A fuel cell 1 according to an embodiment of the present invention is shown in FIG.
This fuel cell 1 has a configuration in which a solid electrolyte membrane 2 is sandwiched between a hydrogen electrode 10 and an air electrode 20.
The solid electrolyte membrane 2 may be made of a proton conductive polymer material, for example, a fluorine-based polymer such as Nafion (trade name of DuPont, hereinafter the same).
水素極１０は反応層１１と拡散層１６を備え、固体電解質膜２へ順に積層される。反応層１１はカーボン粒子等の導電性の担体に白金等の触媒を担持し、電解質でコーティングしたものである。拡散層１６はカーボンペーパー、カーボンクロス、カーボンフェルト等の導電性がありかつガス拡散性能を有する材料から形成される。
空気極２０も反応層２１及び拡散層２６を備える。反応層２１及び拡散層２６の基本構造は、水素極１０のそれらと同じである。
The hydrogen electrode 10 includes a reaction layer 11 and a diffusion layer 16, and is sequentially stacked on the solid electrolyte membrane 2. The reaction layer 11 is formed by supporting a catalyst such as platinum on a conductive carrier such as carbon particles and coating it with an electrolyte. The diffusion layer 16 is formed of a conductive material such as carbon paper, carbon cloth, or carbon felt and having gas diffusion performance.
The air electrode 20 also includes a reaction layer 21 and a diffusion layer 26. The basic structures of the reaction layer 21 and the diffusion layer 26 are the same as those of the hydrogen electrode 10.
この発明では、空気極２０の反応層２１を、図１に示すように、固体電解質膜２側から、第１の層２２、中間層２３及び第２の層２４を順に積層する構成とした。
第１の層２２と第２の層２４にはともに担体に触媒が担持されている。中間層２３には何ら触媒が担持されていない。
In the present invention, the reaction layer 21 of the air electrode 20 has a structure in which a first layer 22, an intermediate layer 23, and a second layer 24 are sequentially laminated from the solid electrolyte membrane 2 side as shown in FIG.
Both the first layer 22 and the second layer 24 have a catalyst supported on a carrier. No catalyst is supported on the intermediate layer 23.
第１の層２２は第２の層２４に比べて保湿性が高く設定されている。
各層の保湿性の制御は、基材、電解質及び触媒の各特性を制御することにより行える。
例えば、カーボン粒子からなる基材の空隙率を高くすることにより保湿性が小さくなる。同様に、担体の撥水性を高めることにより保湿性が小さくなる。
電解質の配合割合を多くすることにより保湿性は高くなる。なお、電解質のＥＷ（スルホン酸基１モル当たりの乾燥重量）を高くすることにより保湿性が低下する。
また、触媒金属の担持密度を高くする事によって、反応層が薄くなり、生成水の発生密度が高まり、乾燥を防止することもできる。
更には親水性の触媒を採用することにより保湿性を高く維持できる。親水性の触媒としてＰｔＣｏ触媒を挙げることができる。また、ＰｔＣｏ触媒を含めて汎用的な触媒を酸処理することにより、その親水性を向上可能である。
上記を考慮して、即ち、基材、電解質及び触媒の少なくとも１つの特性を変えることにより、第１の層２２の保湿性を第２の層２４の保湿性より高くすることができる。
The first layer 22 is set to have higher moisture retention than the second layer 24.
The moisture retention of each layer can be controlled by controlling the characteristics of the substrate, electrolyte, and catalyst.
For example, increasing the porosity of a substrate made of carbon particles reduces the moisture retention. Similarly, moisture retention is reduced by increasing the water repellency of the carrier.
Increasing the blending ratio of the electrolyte increases the moisture retention. In addition, moisture retention falls by raising EW (dry weight per 1 mol of sulfonic acid groups) of electrolyte.
Further, by increasing the supporting density of the catalyst metal, the reaction layer becomes thinner, the generated water generation density increases, and drying can be prevented.
Furthermore, high moisture retention can be maintained by employing a hydrophilic catalyst. An example of the hydrophilic catalyst is a PtCo catalyst. Moreover, the hydrophilicity can be improved by acid-treating a general-purpose catalyst including a PtCo catalyst.
In consideration of the above, that is, by changing at least one characteristic of the substrate, the electrolyte, and the catalyst, the moisture retention of the first layer 22 can be made higher than that of the second layer 24.
低湿度環境で、高性能を得るためには、生成水の持去りを抑制して、電解質膜、及び、発電に寄与する電解質膜近傍の反応層を、湿潤状態に保つことが重要となる。第２の層２４はガス流路に近いため、ガスに生成水が持去られ易く、低湿度環境では、あえて生成水を発生させない、即ち、発電させない方が好ましい。そこで、電解質膜に近い第１の層２２と、流路に近い第２の層２４の間に、触媒を含まない中間層２３を設けて、第１層と第２層の間を、物理的に隔てる構造とすると、第１層の生成水は、中間層により距離を隔てられているため、第２層には拡散し難く、ガスによる持去水量を低減することができる。その結果、電解質膜と第１層のみが湿潤状態に保たれ、低湿度環境でも高性能を発揮する。
他方、高湿度環境で高性能を得るためには、生成水による細孔の閉塞を防止して、反応層全体で発電させることが重要となる。中間層を設けた場合、第１層２２が高保湿性であっても、過剰になった生成水が、中間層に拡散するため、第1の層２２におけるフラッディングの発生を防止できる。
以上の作用を確保する見地から、中間層２３は０．１〜１０μｍ程度の厚さを備えることが好ましい。中間層２３には触媒を担持させないが、製造工程において第1の層２２や第２の層２４から触媒が拡散することがあり、このような意図しない触媒が存在する場合も中間層の定義に含まれるものとする。
In order to obtain high performance in a low humidity environment, it is important to suppress the removal of generated water and keep the electrolyte membrane and the reaction layer in the vicinity of the electrolyte membrane contributing to power generation in a wet state. Since the second layer 24 is close to the gas flow path, the generated water is easily taken away by the gas, and it is preferable not to generate the generated water in a low humidity environment, that is, not to generate power. Therefore, an intermediate layer 23 that does not contain a catalyst is provided between the first layer 22 close to the electrolyte membrane and the second layer 24 close to the flow path, so that the physical layer is physically disposed between the first layer and the second layer. When the structure is separated from each other, the generated water in the first layer is separated by the intermediate layer, so that it is difficult to diffuse into the second layer, and the amount of water taken away by gas can be reduced. As a result, only the electrolyte membrane and the first layer are kept in a wet state, and high performance is exhibited even in a low humidity environment.
On the other hand, in order to obtain high performance in a high humidity environment, it is important to prevent the pores from being clogged with the generated water and generate power in the entire reaction layer. When the intermediate layer is provided, even if the first layer 22 is highly moisturizing, excess generated water diffuses into the intermediate layer, so that flooding in the first layer 22 can be prevented.
From the standpoint of ensuring the above action, the intermediate layer 23 preferably has a thickness of about 0.1 to 10 μm. Although the catalyst is not supported on the intermediate layer 23, the catalyst may diffuse from the first layer 22 or the second layer 24 in the manufacturing process. Even when such an unintended catalyst exists, the definition of the intermediate layer is also included. Shall be included.
以下、この発明の実施例について説明する。
実施例の反応層２１は次の様にして形成される。
先ずは、反応層２１を構成する各層２２，２３，２４のペーストを準備する。
第１の層２２のペーストは、担体としてケッチェンブラックＥＣ６００ＪＤ（ケッチェン・ブラック・インターナショナル（株）の商標名、以下同じ）にＰｔＣｏ合金を触媒として５０ｗ％担持させる。なお、ＰｔとＣｏはモル比で１：３としている。電解質にはナフィオンの５ｗ％溶液を用い、カーボン担体と電解質との重量比は１：１とした。
中間層２３のペーストは、担体としてケッチェンブラックＥＣ（ケッチェン・ブラック・インターナショナル（株）の商標名、以下同じ）を用い、これをナフィオンの５％溶液に分散させる。カーボン担体と電解質との重量比は１：１とした。
第２の層２４のペーストはケッチェンブラックＥＣ６００ＪＤにＰｔ触媒を６０ｗ％担持させる。なお、電解質にはナフィオンの５ｗ％溶液を用い、カーボン担体と電解質との重量比は１：０．８とした。
上記において、第１の層２２と第２の層２４とを比べると、第１の層２２の触媒は第２の層２４の触媒より保湿性が高い。また、基材に対する電解質の配合割合は第１の層２２が第２の層２４より大きい。
Examples of the present invention will be described below.
The reaction layer 21 of the embodiment is formed as follows.
First, a paste of each layer 22, 23, 24 constituting the reaction layer 21 is prepared.
The paste of the first layer 22 carries 50% by weight of PtCo alloy as a catalyst on Ketjen Black EC600JD (trade name of Ketjen Black International Co., Ltd., hereinafter the same) as a carrier. Note that the molar ratio of Pt and Co is 1: 3. A 5 w% solution of Nafion was used as the electrolyte, and the weight ratio of the carbon support to the electrolyte was 1: 1.
For the paste of the intermediate layer 23, Ketjen Black EC (trade name of Ketjen Black International Co., Ltd., hereinafter the same) is used as a carrier, and this is dispersed in a 5% solution of Nafion. The weight ratio between the carbon support and the electrolyte was 1: 1.
The paste of the second layer 24 supports 60% by weight of Pt catalyst on Ketjen Black EC600JD. Note that a 5 w% solution of Nafion was used as the electrolyte, and the weight ratio of the carbon support to the electrolyte was 1: 0.8.
In the above description, when the first layer 22 and the second layer 24 are compared, the catalyst of the first layer 22 has higher moisture retention than the catalyst of the second layer 24. Further, the first layer 22 is larger than the second layer 24 in the ratio of the electrolyte to the base material.
第２の層２４のペーストから順に拡散層２６の表面へ積層し、かつ乾燥して図１に示す反応層２１を構成する。
水素極１０側においても同様にして拡散層１６の表面へ反応層１１を積層する。
水素極１０と空気極２０の各反応層１１、２１を電解質膜２へ貼り合わせて、図１の燃料電池１を構成する。
The reaction layer 21 shown in FIG. 1 is formed by laminating the paste of the second layer 24 in order on the surface of the diffusion layer 26 and drying.
Similarly, the reaction layer 11 is laminated on the surface of the diffusion layer 16 on the hydrogen electrode 10 side.
The reaction layers 11 and 21 of the hydrogen electrode 10 and the air electrode 20 are bonded to the electrolyte membrane 2 to constitute the fuel cell 1 of FIG.
得られた燃料電池１の低加湿環境における出力特性を図２に示す。同様に高加湿環境における出力特性を図３に示す。なお、比較例１は反応層２１の全体を低保湿性の第２の層２４で構成した例、比較例２は反応層２１の全体を高保湿性の第１の層２２で構成した例、比較例３は反応層２１から中間層２３を除去した例である。
図２の低加湿環境とは乾燥空気をプロセス空気として使用した場合であり、図３の高加湿環境とは加湿空気をプロセス空気として使用した場合である。
図２及び図３の結果より、高保湿性である第１の層２２と低保湿性である第２の層２４との間に無触媒の中間層２３を介在させた実施例の燃料電池によれば、低加湿環境及び高加湿環境ともに優れた動作特性を示すことがわかる。
The output characteristics of the obtained fuel cell 1 in a low humidification environment are shown in FIG. Similarly, the output characteristics in a highly humidified environment are shown in FIG. Comparative Example 1 is an example in which the entire reaction layer 21 is configured with a low moisture retention second layer 24, and Comparative Example 2 is an example in which the entire reaction layer 21 is configured with a high moisture retention first layer 22; Comparative Example 3 is an example in which the intermediate layer 23 is removed from the reaction layer 21.
The low humidified environment in FIG. 2 is a case where dry air is used as process air, and the high humidified environment in FIG. 3 is a case where humidified air is used as process air.
2 and 3, the fuel cell of the example in which the non-catalytic intermediate layer 23 is interposed between the first layer 22 having high moisture retention and the second layer 24 having low moisture retention. Thus, it can be seen that both low and high humid environments exhibit excellent operating characteristics.
図４に他の実施例２の燃料電池１００を示す。なお、図１に記載の要素と同一の要素には同一の符号を付してその説明を省略する。
この燃料電池１００では、中間層２３０を三層構造とした。この中間層２３０は高保湿性の第１の層２２に接続する第３−１の層２３１、低保湿性の第２の層２４に接続する第３−２の層２３２及び第３−１の層２３１と第３−２の層２３２に挟まれる第３−３の層２３３からなる。
第３−１の層２３１は、触媒を持たないことの他は第１の層２２の層と同じである。即ち、ケッチェンブラックＥＣ６００ＪＤと電解質としてのナフィオンとを混合し、カーボンと電解質との重量比は１：１である。従って、この第３−１の層２３１の保湿性は第１の層２２とほぼ同じである。
第３−２の層２３２は、触媒を持たないことの他は第２の層２４と同じである。即ち、ケッチェンブラックＥＣ６００ＪＤと電解質としてのナフィオンとを混合し、カーボンと電解質との重量比は１：０．８である。従って、この第３−２の層２３３の保湿性は第２の層２４とほぼ同じである。
第３−３の層２３３は第３−１の層２３１及び第３−２の層２３２よりその保湿性が高くされている。具体的にはケッチェンブラックＥＣ６００ＪＤと酸化チタンを混合し、さらに、電解質としてのナフィオンとを混合し、カーボンと電解質の重量比を１：１.１とした。
触媒を含まない層の保湿性を高くする方法として、上記の酸化チタン、シリカゲル等の親水性材料を混合する以外に、カーボンを熱処理あるいは酸処理して表面を酸化させ親水性とする方法も可能である。さらに、酸化処理したカーボンと親水性材料を混合しても良い。また、酸化スズ、酸化亜鉛等の導電性のある親水性材料をカーボンの代わりに用いることもできる。
FIG. 4 shows a fuel cell 100 of another embodiment 2. The same elements as those described in FIG. 1 are denoted by the same reference numerals and description thereof is omitted.
In the fuel cell 100, the intermediate layer 230 has a three-layer structure. The intermediate layer 230 includes a 3-1 layer 231 connected to the high moisture retention first layer 22, a 3-2 layer 232 connected to the low moisture retention second layer 24, and a 3-1 layer. It consists of a 3-3 layer 233 sandwiched between a layer 231 and a 3-2 layer 232.
The 3-1 layer 231 is the same as the layer of the first layer 22 except that it has no catalyst. That is, Ketjen Black EC600JD and Nafion as an electrolyte are mixed, and the weight ratio of carbon to electrolyte is 1: 1. Therefore, the moisture retaining property of the 3-1 layer 231 is substantially the same as that of the first layer 22.
The third layer 232 is the same as the second layer 24 except that it has no catalyst. That is, Ketjen Black EC600JD and Nafion as an electrolyte are mixed, and the weight ratio of carbon to electrolyte is 1: 0.8. Therefore, the moisture retention of the 3-2 layer 233 is almost the same as that of the second layer 24.
The 3-3 layer 233 has higher moisture retention than the 3-1 layer 231 and the 3-2 layer 232. Specifically, Ketjen Black EC600JD and titanium oxide were mixed, and further Nafion as an electrolyte was mixed to make the weight ratio of carbon and electrolyte 1: 1: 1.
In addition to mixing the above-mentioned hydrophilic materials such as titanium oxide and silica gel as a method for increasing the moisture retention of the layer that does not contain the catalyst, there is also a method that makes the surface hydrophilic by heat treatment or acid treatment of carbon. It is. Further, oxidized carbon and a hydrophilic material may be mixed. In addition, conductive hydrophilic materials such as tin oxide and zinc oxide can be used instead of carbon.
かかる中間層２３０は、これを構成する各層２３１，２３２，２３３のペーストを、第３−２の層から順次第２の層２４へ積層し、かつ乾燥して図４に示す三層構造とする。
図４の例において、水素極１０側の反応層１１は担体としてケッチェンブラックＥＣ６００ＪＤにＰｔを触媒として６０ｗ％担持させる。電解質にはナフィオンの５ｗ％溶液を用い、カーボン担体と電解質との重量比は１：１とした。
The intermediate layer 230 has a three-layer structure shown in FIG. 4 in which the paste of each of the layers 231, 232, and 233 constituting the intermediate layer 230 is sequentially laminated from the 3-2 layer to the second layer 24 and dried. .
In the example of FIG. 4, the reaction layer 11 on the side of the hydrogen electrode 10 supports 60% by weight of Pt as a catalyst on Ketjen Black EC600JD as a carrier. A 5 w% solution of Nafion was used as the electrolyte, and the weight ratio of the carbon support to the electrolyte was 1: 1.
図５の他の実施例３の燃料電池２００を示す。なお、図４と同一の要素には同一の符号を付してその説明を省略する。
この燃料電池２００では、水素極１０側の反応層１１を拡散層１６側から低保湿性の第２の層１４、中間層１３０及び高保湿性の第１の層１２を順次積層した構成とした。ここに中間層１３０を更に三層構造とする、即ち、この中間層１３０は高保湿性の第１の層１２に接続する第３−１の層１３１、低保湿性の第２の層１４に接続する第３−２の層１３２及び第３−１の層１３１と第３−２の層１３２に挟まれる第３−３の層１３３からなる。
6 shows a fuel cell 200 of another embodiment 3 in FIG. The same elements as those in FIG. 4 are denoted by the same reference numerals, and the description thereof is omitted.
In the fuel cell 200, the reaction layer 11 on the hydrogen electrode 10 side is configured by sequentially laminating the second layer 14 with low moisture retention, the intermediate layer 130, and the first layer 12 with high moisture retention from the diffusion layer 16 side. . Here, the intermediate layer 130 further has a three-layer structure. That is, the intermediate layer 130 is divided into a third layer 131 connected to the first layer 12 having high moisture retention and a second layer 14 having low moisture retention. It consists of a third layer 133 and a third layer 132 sandwiched between the third and second layers 132 and 131 and the third and second layers 132 to be connected.
水素極側の反応層１１において第１の層１２は次のように構成される。担体としてケッチェンブラックＥＣ６００ＪＤ（ケッチェン・ブラック・インターナショナル（株）の商標名、以下同じ）にＰｔを触媒として６０ｗ％担持させる。電解質にはナフィオンの５ｗ％溶液を用い、カーボン担体と電解質との重量比は１：１とした。
第２の層１４のペーストはケッチェンブラックＥＣ６００ＪＤにＰｔ触媒を４０ｗ％担持させる。なお、電解質にはナフィオンの５ｗ％溶液を用い、カーボン担体と電解質との重量比は１：０．８とした。
In the reaction layer 11 on the hydrogen electrode side, the first layer 12 is configured as follows. 60% by weight of Pt as a catalyst is supported on Ketjen Black EC600JD (trade name of Ketjen Black International Co., Ltd., hereinafter the same) as a carrier. A 5 w% solution of Nafion was used as the electrolyte, and the weight ratio of the carbon support to the electrolyte was 1: 1.
The paste of the second layer 14 supports 40% by weight of Pt catalyst on Ketjen Black EC600JD. Note that a 5 w% solution of Nafion was used as the electrolyte, and the weight ratio of the carbon support to the electrolyte was 1: 0.8.
中間層１３０の構成は次の通りである。
第３−１の層１３１は、触媒を持たないことの他は第１の層１２の層と同じである。即ち、ケッチェンブラックＥＣ６００ＪＤと電解質としてのナフィオンとを混合し、カーボンと電解質との重量比は１：１である。従って、この第３−１の層１３１の保湿性は第１の層１２とほぼ同じである。
第３−２の層１３２は、触媒を持たないことの他は第２の層１４と同じである。即ち、ケッチェンブラックＥＣ６００ＪＤと電解質としてのナフィオンとを混合し、カーボンと電解質との重量比は１：０．８である。従って、この第３−２の層１３２の保湿性は第２の層１４とほぼ同じである。
第３−３の層１３３は第３−１の層１３１及び第３−２の層１３２よりその保湿性が高くされている。具体的にはケッチェンブラックＥＣ６００ＪＤと酸化チタンを混合し、さらに、電解質としてのナフィオンとを混合し、カーボンと電解質の重量比を１：１．１とした。
かかる中間層１３０は、これを構成する各層１３１，１３２，１３３のペーストを、第３−２の層から順次第２の層１４へ積層し、かつ乾燥して図５に示す三層構造とする。
触媒を含まない層の保湿性を高くする方法として、上記の酸化チタン、シリカゲル等の親水性材料を混合する以外に、カーボンを熱処理あるいは酸処理して表面を酸化させ親水性とする方法も可能である。さらに、酸化処理したカーボンと親水性材料を混合しても良い。また、酸化スズ、酸化亜鉛等の導電性のある親水性材料をカーボンの代わりに用いることもできる。
The configuration of the intermediate layer 130 is as follows.
The 3-1 layer 131 is the same as the layer of the first layer 12 except that it has no catalyst. That is, Ketjen Black EC600JD and Nafion as an electrolyte are mixed, and the weight ratio of carbon to electrolyte is 1: 1. Accordingly, the moisture retention of the 3-1 layer 131 is almost the same as that of the first layer 12.
The 3-2 layer 132 is the same as the 2nd layer 14 except having no catalyst. That is, Ketjen Black EC600JD and Nafion as an electrolyte are mixed, and the weight ratio of carbon to electrolyte is 1: 0.8. Therefore, the moisture retention of the 3-2 layer 132 is substantially the same as that of the second layer 14.
The 3-3 layer 133 has higher moisture retention than the 3-1 layer 131 and the 3-2 layer 132. Specifically, ketjen black EC600JD and titanium oxide were mixed, and Nafion as an electrolyte was further mixed, so that the weight ratio of carbon to the electrolyte was 1: 1.1.
The intermediate layer 130 is formed by laminating the pastes of the respective layers 131, 132, and 133 constituting the intermediate layer 130 sequentially from the 3-2 layer to the second layer 14, and drying to form a three-layer structure shown in FIG. .
In addition to mixing the above-mentioned hydrophilic materials such as titanium oxide and silica gel as a method for increasing the moisture retention of the layer that does not contain the catalyst, there is also a method that makes the surface hydrophilic by heat treatment or acid treatment of carbon. It is. Further, oxidized carbon and a hydrophilic material may be mixed. In addition, conductive hydrophilic materials such as tin oxide and zinc oxide can be used instead of carbon.
図４に示す実施例２の燃料電池１００及び図５に示す実施例３の燃料電池２００の低加湿環境における出力特性を図６に示す。同様に高加湿環境における出力特性を図７に示す。図６及び図７における比較例４は実施例３の燃料電池において、水素極１０及び空気極２０の各反応層１１、２１の全体を低保湿性の第２の層１４、２４で形成したものである。
図６及び図７の結果より、中間層を三層構造にすることにより、特に低加湿環境での燃料電池の出力特性の向上が確認できる。特に、空気極及び水素極の各反応層に中間層を設け、かつその中間層を三層構造とする図５の実施例３では、低加湿環境及び高加湿環境とも優れた出力特性を示す。
FIG. 6 shows output characteristics of the fuel cell 100 of Example 2 shown in FIG. 4 and the fuel cell 200 of Example 3 shown in FIG. 5 in a low humidification environment. Similarly, output characteristics in a highly humidified environment are shown in FIG. 6 and FIG. 7 shows a comparative example 4 in which the entire reaction layers 11 and 21 of the hydrogen electrode 10 and the air electrode 20 are formed by the low moisture retention second layers 14 and 24 in the fuel cell of Example 3. It is.
From the results of FIGS. 6 and 7, it is possible to confirm the improvement of the output characteristics of the fuel cell particularly in a low humidified environment by making the intermediate layer a three-layer structure. In particular, in Example 3 of FIG. 5 in which an intermediate layer is provided in each reaction layer of the air electrode and the hydrogen electrode and the intermediate layer has a three-layer structure, excellent output characteristics are exhibited in both the low and high humidification environments.
上記の例では、各反応層１１、２１をその全面に渡り第１の層−中間層−第２の層なる構成としたが、その面方向の一部のみに当該構造を採用してもよい。
この発明を別の観点からながめれば、反応層においてその厚さ方向に無触媒層を介在させた燃料電池用反応層として把握することができる。
In the above example, each of the reaction layers 11 and 21 is configured to be the first layer-intermediate layer-second layer over the entire surface, but the structure may be adopted only in a part of the surface direction. .
If this invention is looked at from another viewpoint, it can be grasped as a reaction layer for a fuel cell in which a non-catalytic layer is interposed in the thickness direction in the reaction layer.
各層の保湿性の制御には担体の空隙率を調整することが適している。
空隙率を高くしその保湿性を小さくするには、ペーストを水又はアルコールで薄めて拡散層へ塗布すること、電解質/担体の比率を小さくすること、触媒担持密度を高くすること、凍結乾燥させること等が挙げられる。
また、触媒を粉砕することにより層全体としての空隙率を上げることができる。
In order to control the moisture retention of each layer, it is suitable to adjust the porosity of the carrier.
In order to increase the porosity and decrease the moisture retention, the paste is diluted with water or alcohol and applied to the diffusion layer, the electrolyte / support ratio is decreased, the catalyst support density is increased, and lyophilization is performed. And so on.
Further, the porosity of the entire layer can be increased by grinding the catalyst.
本発明は、上記発明の実施の形態及び実施例の説明に何ら限定されるものではない。特許請求の範囲の記載を逸脱せず、当業者が容易に想到できる範囲で種々の変形態様も本発明に含まれる。 The present invention is not limited to the description of the embodiments and examples of the invention described above. Various modifications are also included in the present invention as long as those skilled in the art can easily conceive without departing from the scope of the claims.
１，１００、２００ 燃料電池
２ 固体電解質膜
１０ 水素極
１１ 反応層
１６ 拡散層
２０ 空気極
２１ 反応層
１２、２２ 第１の層
１３０、２３０ 中間層
１４、２４ 第２の層
1, 100, 200 Fuel cell 2 Solid electrolyte membrane 10 Hydrogen electrode 11 Reaction layer 16 Diffusion layer 20 Air electrode 21 Reaction layer 12, 22 First layer 130, 230 Intermediate layer 14, 24 Second layer
Claims (5)
前記固体電解質膜に接する第１の層と、前記拡散層に接する第２の層と、前記第１の層と前記第２の層との間に介在される中間層とを備え、前記第１の層と第２の層は、導電性の単体に担持された触媒を有し、かつ第１の層は前記第２の層より保湿性が高く、前記中間層には触媒が存在しない、ことを特徴とする燃料電池用反応層。 A reaction layer interposed between a solid electrolyte membrane and a diffusion layer in a fuel cell,
A first layer in contact with the solid electrolyte membrane; a second layer in contact with the diffusion layer; and an intermediate layer interposed between the first layer and the second layer, The first layer and the second layer have a catalyst supported on a conductive simple substance, and the first layer has higher moisture retention than the second layer, and the intermediate layer has no catalyst. A reaction layer for a fuel cell.
前記第３−１の層は前記第１の層と同じか若しくはそれより低い保湿性でありかつ前記第３−２の層より高い保湿性を有し、前記第３−２の層は前記第２の層と同じかそれより高い保湿性を有し、前記第３−３の層は前記第３−１の層及び前記第３−２の層より高い保湿性を有する、ことを特徴とする請求項１に記載の燃料電池用反応層。 The intermediate layer includes a 3-1 layer in contact with the first layer, a 3-2 layer in contact with the second layer, the 3-1 layer, and the 3-2 layer. A 3-3 layer sandwiched between
The 3-1 layer has the same or lower moisture retention as the first layer and has a higher moisture retention than the 3-2 layer, and the 3-2 layer is the first layer. The layer 3-3 has the same or higher moisture retention than the second layer, and the 3-3 layer has higher moisture retention than the 3-1 layer and the 3-2 layer. The reaction layer for a fuel cell according to claim 1.
5. The first layer according to claim 1, wherein the first layer has a lower porosity of the carrier, a larger electrolyte ratio, or a lower EW of the electrolyte than the second layer. Reaction layer for fuel cells.
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| US13/381,172 US9325015B2 (en) | 2009-06-29 | 2010-06-29 | Reaction layer for fuel cell |
| CN201080029243.8A CN102484255B (en) | 2009-06-29 | 2010-06-29 | Fuel cell conversion zone |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002015743A (en) * | 2000-06-30 | 2002-01-18 | Asahi Glass Co Ltd | Solid polymer fuel cell |
| JP2002164057A (en) * | 2000-11-28 | 2002-06-07 | Fuji Electric Co Ltd | Solid high molecular fuel cell and method of manufacturing the same |
| JP2005056583A (en) * | 2002-07-09 | 2005-03-03 | Matsushita Electric Ind Co Ltd | Electrolyte membrane-electrode assembly for fuel cell, fuel cell using it, and its manufacturing method |
| JP2005243618A (en) * | 2004-01-26 | 2005-09-08 | Matsushita Electric Ind Co Ltd | Membrane catalyst layer joint body, membrane electrode joint body, and polymer electrolyte type fuel cell |
| JP2006147522A (en) * | 2004-10-21 | 2006-06-08 | Aisin Seiki Co Ltd | Manufacturing method for membrane electrode assembly, fuel cell and manufacturing method for conductive particle layer |
| JP2008153052A (en) * | 2006-12-18 | 2008-07-03 | Matsushita Electric Ind Co Ltd | Membrane electrode assembly for fuel cell and fuel cell using it |
| JP2010021056A (en) * | 2008-07-11 | 2010-01-28 | Toyota Motor Corp | Fuel cell and method for manufacturing same |
| WO2011036749A1 (en) * | 2009-09-24 | 2011-03-31 | 株式会社 東芝 | Collector member, power generation device, and method for producing collector member for power generation device |
| JP2011192593A (en) * | 2010-03-16 | 2011-09-29 | Jx Nippon Oil & Energy Corp | Membrane-electrode assembly and fuel cell |
-
2010
- 2010-03-29 JP JP2010074064A patent/JP5482364B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002015743A (en) * | 2000-06-30 | 2002-01-18 | Asahi Glass Co Ltd | Solid polymer fuel cell |
| JP2002164057A (en) * | 2000-11-28 | 2002-06-07 | Fuji Electric Co Ltd | Solid high molecular fuel cell and method of manufacturing the same |
| JP2005056583A (en) * | 2002-07-09 | 2005-03-03 | Matsushita Electric Ind Co Ltd | Electrolyte membrane-electrode assembly for fuel cell, fuel cell using it, and its manufacturing method |
| JP2005243618A (en) * | 2004-01-26 | 2005-09-08 | Matsushita Electric Ind Co Ltd | Membrane catalyst layer joint body, membrane electrode joint body, and polymer electrolyte type fuel cell |
| JP2006147522A (en) * | 2004-10-21 | 2006-06-08 | Aisin Seiki Co Ltd | Manufacturing method for membrane electrode assembly, fuel cell and manufacturing method for conductive particle layer |
| JP2008153052A (en) * | 2006-12-18 | 2008-07-03 | Matsushita Electric Ind Co Ltd | Membrane electrode assembly for fuel cell and fuel cell using it |
| JP2010021056A (en) * | 2008-07-11 | 2010-01-28 | Toyota Motor Corp | Fuel cell and method for manufacturing same |
| WO2011036749A1 (en) * | 2009-09-24 | 2011-03-31 | 株式会社 東芝 | Collector member, power generation device, and method for producing collector member for power generation device |
| JP2011192593A (en) * | 2010-03-16 | 2011-09-29 | Jx Nippon Oil & Energy Corp | Membrane-electrode assembly and fuel cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5696722B2 (en) * | 2010-03-19 | 2015-04-08 | 旭硝子株式会社 | Membrane electrode assembly for polymer electrolyte fuel cell and method for producing cathode for polymer electrolyte fuel cell |
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