JP2010192160A - Solid alkaline fuel cell, and electrolyte membrane with fixing member and electrode with fixing member for use in the solid alkaline fuel cell - Google Patents

Solid alkaline fuel cell, and electrolyte membrane with fixing member and electrode with fixing member for use in the solid alkaline fuel cell Download PDF

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JP2010192160A
JP2010192160A JP2009032972A JP2009032972A JP2010192160A JP 2010192160 A JP2010192160 A JP 2010192160A JP 2009032972 A JP2009032972 A JP 2009032972A JP 2009032972 A JP2009032972 A JP 2009032972A JP 2010192160 A JP2010192160 A JP 2010192160A
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fixing member
electrolyte membrane
electrode
fuel cell
porous body
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Rei Hiromitsu
礼 弘光
Yasuki Yoshida
安希 吉田
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Dai Nippon Printing Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid alkaline fuel cell improving positional accuracy. <P>SOLUTION: The solid alkaline fuel cell includes: an electrolyte membrane 3; a first fixing member 2 attached to the electrolyte membrane 3 and having an annular recessed part 22; a cathode electrode 5 laminated on an upper surface of the electrolyte membrane 3; a second fixing member 4 attached to the cathode electrode 5 and having an annular projecting part 42 to be engaged to the annular recessed part 22 of the first fixing member 2 when the cathode electrode 5 is laminated on the upper surface of the electrolyte membrane 3; an anode electrode 7 laminated on a lower surface of the electrolyte membrane 3; and a third fixing member 6 attached to the anode electrode 7 and having an annular projecting part 62 to be engaged to the annular recessed part 22 of the first fixing member 2 when the anode electrode 7 is laminated on the lower surface of the electrolyte membrane 3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、固体アルカリ形燃料電池、並びに、これに用いられる固定部材付き電解質膜及び固定部材付き電極に関するものである。   The present invention relates to a solid alkaline fuel cell, and an electrolyte membrane with a fixing member and an electrode with a fixing member used for the same.

固体高分子形燃料電池は、他の燃料電池に比べ、軽量化、高出力密度化等を達成できる観点から、さまざまな研究がなされている。固体高分子形燃料電池は、一般的には、電解質膜としてイオン伝導性高分子電解質膜を用い、その両面に触媒層及び電極基材をそれぞれ順に配置し、更にこれをセパレータで挟んだ構造をしている。   Various studies have been made on polymer electrolyte fuel cells from the viewpoint of achieving weight reduction, higher power density, and the like than other fuel cells. In general, a polymer electrolyte fuel cell uses an ion conductive polymer electrolyte membrane as an electrolyte membrane, and a catalyst layer and an electrode base material are sequentially arranged on both sides of the membrane and further sandwiched between separators. is doing.

この固体高分子形燃料電池は、通常、カチオン(H)を通過させるカチオン伝導性高分子電解質膜を使用する。しかし、近年、高分子電解質膜として、アニオン(OH)を通過させるアニオン伝導性高分子電解質膜を使用した固体アルカリ形燃料電池(「アニオン伝導性固体高分子形燃料電池」とも呼ばれている。)が提案されている(特許文献1)。 This polymer electrolyte fuel cell normally uses a cation conductive polymer electrolyte membrane that allows cations (H + ) to pass therethrough. However, in recent years, a solid alkaline fuel cell using an anion conductive polymer electrolyte membrane that allows anion (OH ) to pass therethrough as a polymer electrolyte membrane (also called “anion conductive solid polymer fuel cell”). Has been proposed (Patent Document 1).

この固体アルカリ形燃料電池を組み立てる方法として、引用文献2には、電解質膜と、アノード電極、及びカソード電極のそれぞれに枠体を取り付け、これらを積層させて各枠体を熱プレスによって一体化する方法が開示されている。   As a method of assembling this solid alkaline fuel cell, in Cited Document 2, a frame is attached to each of the electrolyte membrane, the anode electrode, and the cathode electrode, and these frames are stacked and integrated into each frame by hot pressing. A method is disclosed.

特開2006−244960号公報JP 2006-244960 A 特開平02−278665号公報Japanese Patent Laid-Open No. 02-278665

燃料電池は、その発電効率を高めるためには、電解質膜を挟んだ各電極の位置を互いに一致させることが好ましいが、上述したような燃料電池の組み立て方法では、各電極の位置を合わせることが困難であり、また、熱プレスする際に各電極がずれてしまうなどといったような問題があった。そこで、本発明は、位置精度を向上させることのできる固体アルカリ形燃料電池を提供することを課題とする。   In order to increase the power generation efficiency of the fuel cell, it is preferable to align the positions of the electrodes with the electrolyte membrane interposed therebetween. However, in the fuel cell assembly method as described above, the positions of the electrodes can be aligned. There is a problem that each electrode is displaced during hot pressing. Then, this invention makes it a subject to provide the solid alkaline fuel cell which can improve a positional accuracy.

本発明に係る固体アルカリ形燃料電池は、電解質膜と、前記電解質膜に取り付けられ、被嵌合部を有する第1の固定部材と、前記電解質膜の一方面上に積層されたカソード電極と、前記カソード電極に取り付けられ、前記カソード電極を前記電解質膜の一方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第2の固定部材と、前記電解質膜の他方面上に積層されたアノード電極と、前記アノード電極に取り付けられ、前記アノード電極を前記電解質膜の他方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第3の固定部材と、を備えている。   A solid alkaline fuel cell according to the present invention includes an electrolyte membrane, a first fixing member attached to the electrolyte membrane and having a fitted portion, a cathode electrode laminated on one surface of the electrolyte membrane, A second fixing member attached to the cathode electrode, and having a fitting portion that fits with a fitted portion of the first fixing member when the cathode electrode is laminated on one surface of the electrolyte membrane; An anode electrode laminated on the other surface of the electrolyte membrane, and a fitting portion of the first fixing member attached to the anode electrode when the anode electrode is laminated on the other surface of the electrolyte membrane; A third fixing member having a fitting portion to be fitted.

この固体アルカリ形燃料電池によれば、第2及び第3の固定部材は、嵌合部が第1の固定部材の被嵌合部に嵌合することで第1の固定部材と固定されるため、第1の固定部材に対して常に一定の位置で固定される。このため、第2の固定部材や第3の固定部材が取り付けられたカソード電極やアノード電極は、電解質膜に対して常に一定の位置で積層される。この結果、電解質膜に対するカソード電極及びアノード電極の位置精度を向上させることができる。   According to this solid alkaline fuel cell, the second and third fixing members are fixed to the first fixing member by fitting the fitting portion to the fitted portion of the first fixing member. The first fixing member is always fixed at a fixed position. For this reason, the cathode electrode and the anode electrode to which the second fixing member and the third fixing member are attached are always laminated at a certain position with respect to the electrolyte membrane. As a result, the positional accuracy of the cathode electrode and the anode electrode with respect to the electrolyte membrane can be improved.

上記固体アルカリ形燃料電池は、種々の構成をとることができるが、例えば、第1の固定部材は、中央に開口部を有する枠状であって電解質膜の外周縁部に取り付けられており、前記被嵌合部として両面に環状凹部が形成されており、第2及び第3の固定部材は、嵌合部として環状凹部に嵌合する環状凸部が形成することが好ましい。この構成によれば、一方の電極に供給した燃料ガス又は酸化剤ガスが他方の電極側へ漏出することを、互いに嵌合する環状凸部及び環状凹部によって防止することができ、固体アルカリ形燃料電池のシール性を向上させることができる。   The solid alkaline fuel cell can take various configurations.For example, the first fixing member is a frame having an opening at the center and is attached to the outer peripheral edge of the electrolyte membrane. It is preferable that an annular concave portion is formed on both surfaces as the fitted portion, and the second and third fixing members are formed as an annular convex portion that fits into the annular concave portion as the fitting portion. According to this configuration, the fuel gas or the oxidant gas supplied to one electrode can be prevented from leaking to the other electrode side by the annular convex portion and the annular concave portion that are fitted to each other, and the solid alkaline fuel The sealing property of the battery can be improved.

また、カソード電極及びアノード電極は、多孔質体と、多孔質体の一方面上に形成された触媒層とを有し、触媒層が電解質膜と接触するように電解質膜上に積層され、第2及び第3の固定部材のうち少なくとも一方は、カソード電極またはアノード電極よりも一回り大きく形成され多孔質体の他方面上に接合した天板部を有しており、嵌合部が天板部の外周縁部に形成され、天板部は、多孔質体の他方面が露出するよう複数の貫通孔が形成されていることが好ましい。この構成によれば、天板部に設けられた貫通孔によって燃料ガスや酸化剤ガスを各電極へ供給できるとともに、固体アルカリ形燃料電池の取扱時に各電極に直接触れてしまうことを天板部によって防止でき、ひいては各電極の破損等を防ぐことができる。   The cathode electrode and the anode electrode have a porous body and a catalyst layer formed on one surface of the porous body, and are laminated on the electrolyte membrane so that the catalyst layer is in contact with the electrolyte membrane. At least one of the second and third fixing members has a top plate portion that is formed slightly larger than the cathode electrode or the anode electrode and joined to the other surface of the porous body, and the fitting portion is a top plate. It is preferable that a plurality of through-holes are formed in the top plate portion so that the other surface of the porous body is exposed. According to this configuration, it is possible to supply fuel gas and oxidant gas to each electrode through the through holes provided in the top plate portion, and to directly touch each electrode when handling the solid alkaline fuel cell. By doing so, it is possible to prevent breakage of each electrode.

また、カソード電極に電気的に接続される第1の集電部と、アノード電極に電気的に接続される第2の集電部と、をさらに備えていることが好ましい。   Moreover, it is preferable to further include a first current collector that is electrically connected to the cathode electrode and a second current collector that is electrically connected to the anode electrode.

また、第1の固定部材及び第2の固定部材は、互いに嵌合した際にカソード電極の側面を気密に覆い、第1の固定部材及び第3の固定部材は、互いに嵌合した際にアノード電極の側面を気密に覆うように構成されていることが好ましい。この構成によれば、各電極に供給する燃料ガス及び酸化剤ガスが外部へ漏出することを防止することができる。   The first fixing member and the second fixing member airtightly cover the side surface of the cathode electrode when fitted together, and the first fixing member and the third fixing member are anodes when fitted together. It is preferable that the side surface of the electrode is airtightly covered. According to this configuration, the fuel gas and oxidant gas supplied to each electrode can be prevented from leaking to the outside.

また、本発明に係る固定部材付き電解質膜は、嵌合部を有する固定部材付き電極が積層される、固体アルカリ形燃料電池用の固定部材付き電解質膜であって、電解質膜と、前記電解質膜に取り付けられ、固定部材付き電極の嵌合部と嵌合する被嵌合部を有する固定部材と、を備えている。   An electrolyte membrane with a fixing member according to the present invention is an electrolyte membrane with a fixing member for a solid alkaline fuel cell, in which an electrode with a fixing member having a fitting portion is laminated, and the electrolyte membrane and the electrolyte membrane And a fixing member having a fitted portion to be fitted to the fitting portion of the electrode with the fixing member.

また、本発明に係る固定部材付き電極は、被嵌合部を有する固定部材付き電解質膜に積層される、固体アルカリ形燃料電池用の固定部材付き電極であって、電極と、前記電極に取り付けられ、固定部材付き電解質膜の被嵌合部と嵌合する嵌合部を有する固定部材と、を備えている。   An electrode with a fixing member according to the present invention is an electrode with a fixing member for a solid alkaline fuel cell, which is laminated on an electrolyte membrane with a fixing member having a fitted portion, and is attached to the electrode. And a fixing member having a fitting portion to be fitted to the fitted portion of the electrolyte membrane with the fixing member.

また、本発明に係る他の固体アルカリ形燃料電池は、電解質膜の両面に触媒層が形成された膜触媒層接合体と、前記膜触媒層接合体に取り付けられ、被嵌合部を有する第1の固定部材と、前記膜触媒層の一方面上に積層されたカソード電極用の多孔質体と、前記カソード電極用の多孔質体に取り付けられ、前記カソード電極用の多孔質体を前記膜触媒層接合体の一方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第2の固定部材と、前記膜触媒層の他方面上に積層されたアノード電極用の多孔質体と、前記アノード電極用の多孔質体に取り付けられ、前記アノード電極用の多孔質体を前記膜触媒層接合体の他方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第3の固定部材と、を備えている。   In addition, another solid alkaline fuel cell according to the present invention includes a membrane catalyst layer assembly in which catalyst layers are formed on both surfaces of an electrolyte membrane, and a membrane catalyst layer assembly that is attached to the membrane catalyst layer assembly and has a fitted portion. A cathode member porous body laminated on one surface of the membrane catalyst layer, and the cathode electrode porous body, and the cathode electrode porous body is attached to the membrane. A second fixing member having a fitting portion that fits with a fitted portion of the first fixing member when laminated on one surface of the catalyst layer assembly, and laminated on the other surface of the membrane catalyst layer When the anode electrode porous body is attached to the anode electrode porous body, and the anode electrode porous body is laminated on the other surface of the membrane catalyst layer assembly, the first electrode And a third fixing member having a fitting portion to be fitted to the fitted portion of the fixing member. It is.

この固体アルカリ形燃料電池によれば、第2及び第3の固定部材は、嵌合部が第1の固定部材の被嵌合部に嵌合することで第1の固定部材と固定されるため、第1の固定部材に対して常に一定の位置で固定される。このため、第2の固定部材や第3の固定部材が取り付けられたカソード電極用の多孔質やアノード電極用の多孔質は、第1の固定部材が取り付けられた膜触媒層接合体に対して常に一定の位置で積層される。この結果、膜触媒層接合体に対するカソード電極用の多孔質体及びアノード電極用の多孔質体の位置精度を向上させることができる。   According to this solid alkaline fuel cell, the second and third fixing members are fixed to the first fixing member by fitting the fitting portion to the fitted portion of the first fixing member. The first fixing member is always fixed at a fixed position. For this reason, the porous for the cathode electrode and the porous for the anode electrode to which the second fixing member and the third fixing member are attached are compared with the membrane-catalyst layer assembly to which the first fixing member is attached. It is always laminated at a certain position. As a result, it is possible to improve the positional accuracy of the porous body for the cathode electrode and the porous body for the anode electrode with respect to the membrane catalyst layer assembly.

本発明によれば、位置精度を向上させることのできる固体アルカリ形燃料電池を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the solid alkaline fuel cell which can improve a positional accuracy can be provided.

図1は本発明に係る固体アルカリ形燃料電池の実施形態を示す正面断面図である。FIG. 1 is a front sectional view showing an embodiment of a solid alkaline fuel cell according to the present invention. 図2は本発明に係る固定部材付き電解質膜の実施形態を示す正面断面図である。FIG. 2 is a front sectional view showing an embodiment of the electrolyte membrane with a fixing member according to the present invention. 図3は本発明に係る固定部材付き電解質膜の実施形態を示す平面図である。FIG. 3 is a plan view showing an embodiment of an electrolyte membrane with a fixing member according to the present invention. 図4は本発明に係る固定部材付き電極の実施形態を示す正面断面図である。FIG. 4 is a front sectional view showing an embodiment of an electrode with a fixing member according to the present invention. 図5は本発明に係る固定部材付き電極の実施形態を示す平面図である。FIG. 5 is a plan view showing an embodiment of an electrode with a fixing member according to the present invention. 図6は本発明に係る固定部材付き電極の実施形態を示す底面図である。FIG. 6 is a bottom view showing an embodiment of an electrode with a fixing member according to the present invention. 図7は本発明に係る固定部材付き電極の実施形態を示す正面断面図である。FIG. 7 is a front sectional view showing an embodiment of an electrode with a fixing member according to the present invention. 図8は本発明に係る固体アルカリ形燃料電池の組み立て前の実施形態を示す正面断面図である。FIG. 8 is a front sectional view showing an embodiment before assembly of the solid alkaline fuel cell according to the present invention. 図9は本実施形態に係る固体アルカリ形燃料電池の使用方法を示す正面断面図である。FIG. 9 is a front sectional view showing a method of using the solid alkaline fuel cell according to the present embodiment. 図10は本発明に係る固定部材付き電極の他の実施形態を示す正面断面図である。FIG. 10 is a front sectional view showing another embodiment of the electrode with a fixing member according to the present invention. 図11は本発明に係る固体アルカリ形燃料電池の組み立て前の他の実施形態を示す正面断面図である。FIG. 11 is a front sectional view showing another embodiment before assembly of the solid alkaline fuel cell according to the present invention.

以下、本発明に係る固体アルカリ形燃料電池の実施形態について図面を参照しつつ説明する。   Hereinafter, embodiments of a solid alkaline fuel cell according to the present invention will be described with reference to the drawings.

図1に示すように、固体アルカリ形燃料電池1は、第1の固定部材2が取り付けられた電解質膜3と、第2の固定部材4が取り付けられたカソード電極5と、第3の固定部材6が取り付けられたアノード電極7と、を備えている。   As shown in FIG. 1, a solid alkaline fuel cell 1 includes an electrolyte membrane 3 to which a first fixing member 2 is attached, a cathode electrode 5 to which a second fixing member 4 is attached, and a third fixing member. And an anode electrode 7 to which 6 is attached.

図2及び図3に示すように、電解質膜3は、平面視矩形状であり、厚さは、後述する多孔質体の種類や触媒層の厚さ等を考慮して適宜決定するが、通常、20〜200μm程度、好ましくは25〜75μm程度である。この電解質膜3の外周縁部には、第1の固定部材2が一体的に取り付けられている。第1の固定部材2は、略枠状であって中央に開口部21を有しており、上面及び下面には環状凹部(被嵌合部)22が形成されている。   As shown in FIG. 2 and FIG. 3, the electrolyte membrane 3 has a rectangular shape in plan view, and the thickness is appropriately determined in consideration of the kind of the porous body and the thickness of the catalyst layer described later. It is about 20-200 micrometers, Preferably it is about 25-75 micrometers. A first fixing member 2 is integrally attached to the outer peripheral edge of the electrolyte membrane 3. The first fixing member 2 has a substantially frame shape and has an opening 21 at the center, and an annular recess (fitting portion) 22 is formed on the upper surface and the lower surface.

図4〜図6に示すように、カソード電極5は、平面視矩形状で導電性を有する多孔質体51と、多孔質体51の下面に形成された触媒層52とを有している。多孔質体51の厚さは、100〜500μm程度とすることが好ましく、200〜400μm程度とすることがより好ましい。また、触媒層52の厚さは、多孔質体51の種類や電解質膜3の厚さ等を考慮して適宜決定すればよいが、通常10μm〜200μm程度、好ましくは10μm〜100μm程度、より好ましくは15μm〜50μm程度がよい。   As shown in FIGS. 4 to 6, the cathode electrode 5 includes a porous body 51 having a rectangular shape in plan view and conductivity, and a catalyst layer 52 formed on the lower surface of the porous body 51. The thickness of the porous body 51 is preferably about 100 to 500 μm, and more preferably about 200 to 400 μm. The thickness of the catalyst layer 52 may be appropriately determined in consideration of the type of the porous body 51, the thickness of the electrolyte membrane 3, etc., but is usually about 10 μm to 200 μm, preferably about 10 μm to 100 μm, more preferably. Is preferably about 15 μm to 50 μm.

このように多孔質体51及び触媒層52から構成されたカソード電極5には、第2の固定部材4が取り付けられている。第2の固定部材4は、多孔質体51よりも一回り大きく形成された平面視矩形状の天板部41を有しており、この天板部41の下面と多孔質体51の上面とが接合することで、第2の固定部材4がカソード電極5に取り付けられている。また、天板部41には複数の貫通孔43が形成されており、この貫通孔43によってカソード電極5に酸化剤ガスを供給することができる。この貫通孔43は、特に限定されるものではないが、例えば、ドリルやパンチ、レザー刃、トムソン刃、レーザー加工などによって、形成することができる。また、貫通孔43の開口率(天板部41のカソード電極5に対応する部分に形成された貫通孔43の開口面積の総和をカソード電極5の面積で割ったもの)は、特に限定されるものではないが、45〜98%とすることが好ましい。天板部41の外周縁には、下方に延びる環状凸部(嵌合部)42が形成されている。この環状凸部42と上述した第1の固定部材2の環状凹部22とが嵌合することによって、第1の固定部材2と第2の固定部材4とが気密に一体化する。環状凸部42と環状凹部22の幅と深さは、特に限定されるものではないが、環状凸部42の凸部の幅は、0.3〜15mmが好ましく、また、環状凹部22の凹部の幅は、環状凸部42の凸部の幅よりも0.5〜3mm大きく形成されているほうが好ましい。環状凹部22の幅を環状凸部42よりも0.5mm以上大きく形成することで環状凸部42を環状凹部22にスムーズに嵌合させることができ、また、環状凹部22の幅を環状凸部42の幅より3mm以上大きくしないことで機密性を十分に保つことができる。深さを0.3mm以上とすることで、機密性を十分に保つことができる。また、嵌合部にツメを形成することで、機密性をあげることができる。なお、天板部41の厚さは、0.5mm〜10mm程度とすることが好ましく、1mm〜5mmとすることがより好ましい。   Thus, the second fixing member 4 is attached to the cathode electrode 5 composed of the porous body 51 and the catalyst layer 52. The second fixing member 4 has a top plate portion 41 having a rectangular shape in plan view formed slightly larger than the porous body 51. The lower surface of the top plate portion 41, the upper surface of the porous body 51, and As a result of joining, the second fixing member 4 is attached to the cathode electrode 5. In addition, a plurality of through holes 43 are formed in the top plate portion 41, and an oxidant gas can be supplied to the cathode electrode 5 through the through holes 43. Although this through-hole 43 is not specifically limited, For example, it can be formed by a drill, a punch, a leather blade, a Thomson blade, laser processing etc. Further, the aperture ratio of the through-hole 43 (the sum of the opening area of the through-hole 43 formed in the portion corresponding to the cathode electrode 5 of the top plate portion 41 divided by the area of the cathode electrode 5) is particularly limited. Although it is not a thing, it is preferable to set it as 45 to 98%. An annular convex portion (fitting portion) 42 extending downward is formed on the outer peripheral edge of the top plate portion 41. By fitting the annular convex portion 42 and the annular concave portion 22 of the first fixing member 2 described above, the first fixing member 2 and the second fixing member 4 are integrated in an airtight manner. The width and depth of the annular convex portion 42 and the annular concave portion 22 are not particularly limited, but the width of the convex portion of the annular convex portion 42 is preferably 0.3 to 15 mm. The width is preferably 0.5-3 mm larger than the width of the convex portion of the annular convex portion 42. By forming the width of the annular recess 22 larger than the annular projection 42 by 0.5 mm or more, the annular projection 42 can be smoothly fitted into the annular recess 22, and the width of the annular recess 22 can be reduced to the annular projection. Confidentiality can be maintained sufficiently by not making it larger than the width of 42 by 3 mm or more. By setting the depth to 0.3 mm or more, confidentiality can be sufficiently maintained. Moreover, confidentiality can be raised by forming a nail | claw in a fitting part. In addition, it is preferable that the thickness of the top plate part 41 shall be about 0.5 mm-10 mm, and it is more preferable to set it as 1 mm-5 mm.

図7に示すように、アノード電極7は、カソード電極5と同じ構成をしており、平面視矩形状で導電性を有する多孔質体71と、多孔質体71の上面に形成された触媒層72とを有している。多孔質体71の厚さは、200μm〜2mm程度、好ましくは300〜600μm程度である。また、触媒層72の好ましい厚さの範囲は上記カソード電極5の触媒層52と同じである。アノード電極7には第3の固定部材6が取り付けられているが、この第3の固定部材6も、複数の貫通孔63が形成された天板部61と、環状凸部(嵌合部)62を有しており、上記第2の固定部材4と同じ構成となっている。   As shown in FIG. 7, the anode electrode 7 has the same configuration as the cathode electrode 5, has a rectangular shape in plan view and has conductivity, and a catalyst layer formed on the upper surface of the porous body 71. 72. The thickness of the porous body 71 is about 200 μm to 2 mm, preferably about 300 to 600 μm. The preferable thickness range of the catalyst layer 72 is the same as that of the catalyst layer 52 of the cathode electrode 5. A third fixing member 6 is attached to the anode electrode 7. The third fixing member 6 also includes a top plate portion 61 in which a plurality of through holes 63 are formed, and an annular convex portion (fitting portion). 62 and has the same configuration as the second fixing member 4.

次に、上述した固体アルカリ形燃料電池を構成する各部材の材料について説明する。   Next, the material of each member constituting the solid alkaline fuel cell described above will be described.

電解質膜3はアニオン伝導性高分子電解質膜を使用するが、このアニオン伝導性高分子電解質膜として、例えば、炭化水素系又はフッ素樹脂系のいずれかを用いることができる。電解質膜3に高濃度のアルカリ水溶液を含浸させる場合は、耐アルカリ性の観点から、フッ素樹脂系電解質膜を使用することが好ましい。なお、耐アルカリ性のフッ素樹脂系電解質膜を用いることにより、アニオン伝導性を向上させることができる。低濃度のアルカリ水溶液を使用する場合、又はアルカリ水溶液を使用しない場合は、低コスト化の観点から、炭化水素系電解質膜を用いることが好ましい。なお、アルカリ水溶液としては、例えば、KOH溶液、NaOH溶液などを挙げることができる。また、上記高濃度とは、使用するアルカリ水溶液の種類等によって適宜変更するが、本説明では、2モル/l程度以上をいい、低濃度とは、2モル/l程度以下をいう。フッ素樹脂系電解質膜の具体例としては、例えば東ソー(株)製のトスフレックス(登録商標)IE−SF34等が挙げられる。炭化水素系電解質膜の具体例としては、例えば、旭化成(株)製のアシプレックス(登録商標)A−201、211,221や、トクヤマ(株)製のネオセプタ(登録商標)AM−1、AHA等が挙げられる。   The electrolyte membrane 3 uses an anion conductive polymer electrolyte membrane. As the anion conductive polymer electrolyte membrane, for example, either a hydrocarbon type or a fluororesin type can be used. When the electrolyte membrane 3 is impregnated with a high concentration alkaline aqueous solution, it is preferable to use a fluororesin-based electrolyte membrane from the viewpoint of alkali resistance. In addition, anion conductivity can be improved by using an alkali-resistant fluorine resin electrolyte membrane. When using a low concentration alkaline aqueous solution or not using an alkaline aqueous solution, it is preferable to use a hydrocarbon-based electrolyte membrane from the viewpoint of cost reduction. Examples of the alkaline aqueous solution include a KOH solution and a NaOH solution. Moreover, although the said high concentration changes suitably with the kind etc. of aqueous alkali solution to be used etc., in this description, about 2 mol / l or more is said, and a low concentration means about 2 mol / l or less. Specific examples of the fluororesin-based electrolyte membrane include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation. Specific examples of the hydrocarbon-based electrolyte membrane include, for example, Aciplex (registered trademark) A-201, 211, 221 manufactured by Asahi Kasei Co., Ltd., Neoceptor (registered trademark) AM-1, AHA manufactured by Tokuyama Corporation. Etc.

カソード電極5に用いられる多孔質体51としては、例えば、カーボンペーパやカーボンクロス、カーボン繊維からなる不織布等を使用することができる。このカソード電極5に用いられる多孔質体51の気孔率は、75〜98%程度とすることが好ましく、80〜95%程度とすることがより好ましい。   As the porous body 51 used for the cathode electrode 5, for example, carbon paper, carbon cloth, a nonwoven fabric made of carbon fiber, or the like can be used. The porosity of the porous body 51 used for the cathode electrode 5 is preferably about 75 to 98%, more preferably about 80 to 95%.

アノード電極7に用いられる多孔質体71は、金属製のものを用いることが好ましい。このような金属製の多孔質体71としては、例えば、発泡ニッケルやクロム含有発泡ニッケル、発泡チタン、発泡銀等を挙げることができる。このアノード電極7用の多孔質体71の気孔率は、75〜98%程度とすることが好ましく、80〜95%程度とすることがより好ましい。また、多孔質体71の気孔の最大径である呼び口径は30〜700μm程度、好ましくは50〜300μm程度である。   The porous body 71 used for the anode electrode 7 is preferably made of a metal. Examples of such a metal porous body 71 include foamed nickel, chromium-containing foamed nickel, foamed titanium, and foamed silver. The porosity of the porous body 71 for the anode electrode 7 is preferably about 75 to 98%, more preferably about 80 to 95%. Moreover, the nominal diameter which is the maximum diameter of the pores of the porous body 71 is about 30 to 700 μm, preferably about 50 to 300 μm.

カソード電極5及びアノード電極7に用いられる触媒層52,72は、触媒及びアニオン伝導性高分子電解質を含有する。触媒及びアニオン伝導性高分子電解質の含有量(重量比)は特に限定されるものではないが、好ましくは、触媒:アニオン伝導性高分子電解質=5:1〜1:4程度、より好ましくは、3:1〜1:3程度である。なお、カソード電極5に用いる触媒層52とアノード電極7に用いる触媒層72とは同一成分であってもよく、異なる成分であってもよい。   The catalyst layers 52 and 72 used for the cathode electrode 5 and the anode electrode 7 contain a catalyst and an anion conductive polymer electrolyte. The content (weight ratio) of the catalyst and the anion conductive polymer electrolyte is not particularly limited, but preferably, catalyst: anion conductive polymer electrolyte = about 5: 1 to 1: 4, more preferably It is about 3: 1 to 1: 3. The catalyst layer 52 used for the cathode electrode 5 and the catalyst layer 72 used for the anode electrode 7 may be the same component or different components.

上記触媒層52,72に含有される触媒は、通常、触媒金属微粒子が担体に担持されてなるものであり、公知又は市販のものを使用することができる。   The catalyst contained in the catalyst layers 52 and 72 is usually formed by supporting catalyst metal fine particles on a carrier, and a known or commercially available catalyst can be used.

触媒金属微粒子は、例えば白金、鉄、コバルト、ニッケル、パラジウム、銀、ルテニウム、イリジウム、モリブデン、マンガンが挙げられ、これら2種以上の合金であってもよい。触媒金属微粒子が2種以上からなる合金である場合は、白金、鉄、コバルト、ニッケルのうち少なくとも2種以上含有することが好ましい。このような合金の例としては、例えば、白金−鉄合金、白金−コバルト合金、鉄−コバルト合金、コバルト−ニッケル合金、鉄−ニッケル合金等のほか、鉄−コバルト−ニッケル合金が挙げられる。これらの金属の各比率は限定的でなく、幅広い範囲から適宜選択できる。また、触媒金属微粒子の粒径は限定的でないが、通常0.05〜20nm程度、好ましくは0.1〜10nm程度、最も好ましくは0.3〜5nm程度である。なお、触媒金属微粒子の粒径は、例えば、X線回折における触媒成分の回折ピークの半値幅により求められる結晶粒子径、又は透過型電子顕微鏡像により調べられる触媒成分の粒子径によって測定することができる。   Examples of the catalyst metal fine particles include platinum, iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum, and manganese, and these two or more kinds of alloys may be used. When the catalyst metal fine particles are an alloy composed of two or more kinds, it is preferable to contain at least two kinds of platinum, iron, cobalt, and nickel. Examples of such alloys include platinum-iron alloys, platinum-cobalt alloys, iron-cobalt alloys, cobalt-nickel alloys, iron-nickel alloys, and the like, as well as iron-cobalt-nickel alloys. Each ratio of these metals is not limited and can be appropriately selected from a wide range. The particle diameter of the catalytic metal fine particles is not limited, but is usually about 0.05 to 20 nm, preferably about 0.1 to 10 nm, and most preferably about 0.3 to 5 nm. The particle diameter of the catalyst metal fine particles can be measured by, for example, the crystal particle diameter obtained from the half-value width of the diffraction peak of the catalyst component in X-ray diffraction, or the particle diameter of the catalyst component examined by a transmission electron microscope image. it can.

触媒金属微粒子が担持される担体は限定的でなく、公知又は市販のものが使用でき、例えば、アルミナ粒子、シリカ粒子、炭素粒子等が挙げられる。耐食性及び導電性の観点から、炭素粒子(特に導電性炭素粒子)が好ましい。この導電性炭素粒子としては、例えば、アセチレンブラック、ファーネスブラック、チャンネルブラック、ケッチェンブラック等のカーボンブラックのほか、黒鉛、活性炭、カーボン繊維、カーボンナノチューブ、カーボンナノワイヤー等が挙げられ、これらを1種又は2種以上使用してもよい。炭素粒子の比表面積は限定されないが、通常10〜1500m/g程度、好ましくは10〜500m/g程度である。粒径は、一般的には平均一次粒子径として0.01〜1μm程度、好ましくは0.01〜0.2μm程度とすることが好ましい。なお、導電性炭素粒子の粒径は、例えば、レーザ回折装置による粒度分布計や透過型電子顕微鏡像により調べられる導電性炭素の粒子径によって測定することができる。
触媒金属微粒子の担持量は、触媒金属微粒子及び担体の種類等によって適宜決定されるが、担体100重量部に対して、通常、1〜80重量部程度、好ましくは3〜50重量部程度とすればよい。
The carrier on which the catalyst metal fine particles are supported is not limited, and a known or commercially available carrier can be used, and examples thereof include alumina particles, silica particles, and carbon particles. From the viewpoint of corrosion resistance and conductivity, carbon particles (particularly conductive carbon particles) are preferred. Examples of the conductive carbon particles include carbon black such as acetylene black, furnace black, channel black, ketjen black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon nanowire, and the like. You may use a seed | species or 2 or more types. The specific surface area of the carbon particles is not limited, but is usually about 10 to 1500 m 2 / g, preferably about 10 to 500 m 2 / g. The particle size is generally about 0.01 to 1 μm, preferably about 0.01 to 0.2 μm, as the average primary particle size. The particle size of the conductive carbon particles can be measured by, for example, the particle size of the conductive carbon examined by a particle size distribution meter using a laser diffraction apparatus or a transmission electron microscope image.
The amount of the catalyst metal fine particles supported is appropriately determined depending on the type of the catalyst metal fine particles and the carrier, but is usually about 1 to 80 parts by weight, preferably about 3 to 50 parts by weight with respect to 100 parts by weight of the carrier. That's fine.

また、触媒層52,72に含有されるアニオン伝導性高分子電解質は、アニオンとして水酸基イオン(OHイオン)を伝導できる電解質であればよく、公知又は市販のものを使用でき、例えば、炭化水素系及びフッ素樹脂系のいずれの電解質を用いることができる。炭化水素系の電解質としては、例えば、芳香族ポリエーテルスルホン酸と芳香族ポリチオエーテルスルホン酸との共重合体のクロロメチル化物をアミノ化して得られる電解質等が挙げられる。また、フッ素樹脂系の電解質としては、例えば、スルホン酸基を有するパーフルオロカーボンポリマーの末端をジアミンで処理し4級化したポリマーや、ポリクロロメチルスルチレンの4級化物等のポリマー等が挙げられ、特に、溶媒可溶性のものが好ましい。 The anion conductive polymer electrolyte contained in the catalyst layers 52 and 72 may be any electrolyte that can conduct hydroxyl ion (OH - ion) as an anion, and any known or commercially available one can be used. Any electrolyte of the type and fluororesin type can be used. Examples of the hydrocarbon electrolyte include an electrolyte obtained by aminating a chloromethylated product of a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid. Examples of the fluororesin-based electrolyte include a polymer obtained by treating the terminal of a perfluorocarbon polymer having a sulfonic acid group with a diamine and quaternizing it, a polymer such as a quaternized product of polychloromethylsulfylene, and the like. In particular, a solvent-soluble one is preferable.

上記電解質は、例えば特開2003−86193号公報、特開2000−331693号公報で開示されたものを使用すればよい。より具体的に説明すると、クロロメチル化は、芳香族ポリエーテルスルホン酸と芳香族ポリチオエーテルスルホン酸との共重合体にクロロメチル化剤を反応させて行う。クロロメチル化剤としては、例えば、(クロロメトキシ)メタン、1,4−ビス(クロロメトキシ)ブタン、1−クロロメトキシ−4−クロロブタン、ホルムアルデヒド−塩化水素、パラホルムアルデヒド−塩化水素等が使用できる。このようにして得られたクロロメチル化物を、アミン化合物と反応させてアニオン交換基を導入する。アミン化合物としては、例えば、モノアミン、1分子中に2個以上のアミノ基を有するポリアミン化合物等が使用できる。具体的にはアンモニアの他、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン等のモノアルキルアミン、ジメチルアミン、ジエチルアミン等のジアルキルアミン、アニリン、N−メチルアニリン等の芳香族アミン、ピロリジン、ピペラジン、モルホリン等の複素環アミン等のモノアミンや、m−フェニレンジアミン、ピリダジン、ピリミジン等のポリアミン化合物が使用できる。これらアニオン伝導性高分子電解質は通常アルコール、エーテル等の有機溶剤又は有機溶剤と水との混合溶剤に5〜30重量%の濃度で分散されている。   What is necessary is just to use what was disclosed by Unexamined-Japanese-Patent No. 2003-86193 and Unexamined-Japanese-Patent No. 2000-331693, for example. More specifically, chloromethylation is carried out by reacting a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid with a chloromethylating agent. As the chloromethylating agent, for example, (chloromethoxy) methane, 1,4-bis (chloromethoxy) butane, 1-chloromethoxy-4-chlorobutane, formaldehyde-hydrogen chloride, paraformaldehyde-hydrogen chloride and the like can be used. The chloromethylated product thus obtained is reacted with an amine compound to introduce an anion exchange group. As the amine compound, for example, a monoamine, a polyamine compound having two or more amino groups in one molecule, and the like can be used. Specifically, in addition to ammonia, monoalkylamines such as methylamine, ethylamine, propylamine and butylamine, dialkylamines such as dimethylamine and diethylamine, aromatic amines such as aniline and N-methylaniline, pyrrolidine, piperazine and morpholine Monoamines such as heterocyclic amines, and polyamine compounds such as m-phenylenediamine, pyridazine, and pyrimidine can be used. These anion conductive polymer electrolytes are usually dispersed at a concentration of 5 to 30% by weight in an organic solvent such as alcohol or ether or a mixed solvent of an organic solvent and water.

また、触媒層52,72は、上述した触媒及びアニオン伝導性高分子電解質に加えてさらに、フッ素系樹脂を含有してもよい。このフッ素系樹脂を含有することにより、上記成分の結着性が向上し、より強固な触媒層となると同時に撥水性を付与することができる。このフッ素系樹脂としては、例えば、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、フッ化ビニリデン−六フッ化プロピレン共重合体等が挙げられる。これらの中でも、より結着性及び撥水性が良好な点から、ポリテトラフルオロエチレンが好ましい。フッ素系樹脂を含有する場合の含有量は、触媒100重量部に対して、通常5〜25重量部程度、好ましくは10〜15重量部程度である。   Moreover, the catalyst layers 52 and 72 may further contain a fluorine-based resin in addition to the above-described catalyst and anion conductive polymer electrolyte. By containing this fluororesin, the binding property of the above components is improved, and a stronger catalyst layer can be provided and at the same time water repellency can be imparted. Examples of the fluororesin include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and the like. Among these, polytetrafluoroethylene is preferable from the viewpoint of better binding and water repellency. The content of the fluororesin is usually about 5 to 25 parts by weight, preferably about 10 to 15 parts by weight with respect to 100 parts by weight of the catalyst.

第1〜第3の固定部材2,4,6は、公知又は市販品の熱硬化性樹脂を用いることができる。例えば、エポキシ樹脂、メラミン樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリエチレン樹脂(PE)、高密度ポリエチレン樹脂(HDPE)、中密度ポリエチレン樹脂(MDPE)、低密度ポリエチレン樹脂(LDPE)、ポリプロピレン樹脂(PP)、ポリスチレン(PS)、ポリ酢酸ビニル(PVAc)、ABS樹脂(アクリロニトリルブタジエンスチレン樹脂)、AS樹脂、アクリル樹脂(PMMA)等を使用することができる。   For the first to third fixing members 2, 4, and 6, known or commercially available thermosetting resins can be used. For example, epoxy resin, melamine resin, phenol resin, unsaturated polyester resin, polyethylene resin (PE), high density polyethylene resin (HDPE), medium density polyethylene resin (MDPE), low density polyethylene resin (LDPE), polypropylene resin (PP ), Polystyrene (PS), polyvinyl acetate (PVAc), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), and the like.

次に上述した固体アルカリ形燃料電池の製造方法について説明する。   Next, a method for manufacturing the above-described solid alkaline fuel cell will be described.

まず、電解質膜3に第1の固定部材2を取り付ける。この取り付け方法は、種々の方法を採用することができるが、例えば、電解質膜3を金型内に配置し、金型内に射出成形によって上述した樹脂を充填して第1の固定部材2を成形することによって電解質膜3に第1の固定部材2を取り付けることができる。また、その他にも、トランスファー成形やインサート成形、モールド成形、二色成形などの公知の技術で電解質膜3に第1の固定部材2を取り付けることができる。   First, the first fixing member 2 is attached to the electrolyte membrane 3. For this attachment method, various methods can be adopted. For example, the electrolyte membrane 3 is arranged in a mold, and the resin is filled in the mold by injection molding, so that the first fixing member 2 is fixed. The first fixing member 2 can be attached to the electrolyte membrane 3 by molding. In addition, the first fixing member 2 can be attached to the electrolyte membrane 3 by a known technique such as transfer molding, insert molding, molding, or two-color molding.

次に、カソード電極5に第2の固定部材4を、また、アノード電極7に第3の固定部材6を取り付ける。この各電極5,7への固定部材4,6の取り付けは、まず、上述した電解質膜3に第1の固定部材2を取り付ける方法と同様の方法で、多孔質体51に第2の固定部材4を、また、多孔質体71に第3の固定部材6を取り付ける。そして、各固定部材4,6が取り付けられた各多孔質体51、71に、触媒層52、72を形成する。   Next, the second fixing member 4 is attached to the cathode electrode 5, and the third fixing member 6 is attached to the anode electrode 7. The fixing members 4 and 6 are attached to the electrodes 5 and 7 in the same manner as the method for attaching the first fixing member 2 to the electrolyte membrane 3 described above, and the second fixing member is attached to the porous body 51. 4, and the third fixing member 6 is attached to the porous body 71. Then, catalyst layers 52 and 72 are formed on the porous bodies 51 and 71 to which the fixing members 4 and 6 are attached, respectively.

多孔質体51,71に触媒層52,72を形成する方法は、例えば、上述した触媒及びアニオン伝導性高分子電解質を粘度調整用の溶剤に分散させて触媒層形成用ペースト組成物を調整し、これを多孔質体51,71に塗布して乾燥して多孔質体51,71上に触媒層52,72を形成する。なお、触媒層形成用ペースト組成物の塗布方法としては、特に限定されるものではないが、例えば、ナイフコーターや、バーコーター、スプレー、ディップコーター、スピンコーター、ロールコーター、ダイコーター、カーテンコーター、スクリーン印刷などの一般的な方法を挙げることができる。また、触媒層形成用ペースト組成物を塗布した後の乾燥温度は、通常40〜100℃程度、好ましくは60〜80℃程度であり、乾燥時間は、乾燥温度にもよるが、通常5分〜2時間程度、好ましくは30分〜1時間程度である。また、粘度調整用の溶剤は、特に限定されるものではなく、広い範囲内で適宜選択される。例えば、各種アルコールや、各種エーテル、各種ジアルキルスルホキシド、水、又はこれらの混合物を使用することができる。これら溶剤の中でも、アルコールが好ましく、アルコールとしては、例えば、メタノール、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、tert−ブタノール等の炭素数1〜4の一価アルコール及びプロピレングリコール、ジエチレングリコール等の多価アルコールが挙げられる。また、触媒層形成用ペースト組成物の配合割合は広い範囲内で適宜選択することができるが、例えば、触媒1重量部に対して、アニオン伝導性高分子電解質(固形分)1〜3重量部、粘度調整用の溶剤1〜100重量部程度とすることができる。   The method for forming the catalyst layers 52 and 72 on the porous bodies 51 and 71 includes, for example, preparing the catalyst layer forming paste composition by dispersing the catalyst and the anion conductive polymer electrolyte in a viscosity adjusting solvent. This is applied to the porous bodies 51 and 71 and dried to form the catalyst layers 52 and 72 on the porous bodies 51 and 71. The method for applying the catalyst layer forming paste composition is not particularly limited. For example, knife coaters, bar coaters, sprayers, dip coaters, spin coaters, roll coaters, die coaters, curtain coaters, General methods such as screen printing can be mentioned. Moreover, the drying temperature after apply | coating the paste composition for catalyst layer formation is about 40-100 degreeC normally, Preferably it is about 60-80 degreeC, Although drying time is based also on drying temperature, normally 5 minutes- About 2 hours, preferably about 30 minutes to 1 hour. The viscosity adjusting solvent is not particularly limited, and is appropriately selected within a wide range. For example, various alcohols, various ethers, various dialkyl sulfoxides, water, or a mixture thereof can be used. Among these solvents, alcohol is preferable, and examples of alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, and other monohydric alcohols such as propylene glycol and diethylene glycol. A polyhydric alcohol is mentioned. The blending ratio of the catalyst layer forming paste composition can be appropriately selected within a wide range. For example, 1 part by weight of the catalyst is 1 to 3 parts by weight of the anion conductive polymer electrolyte (solid content). The viscosity adjusting solvent can be about 1 to 100 parts by weight.

以上のように形成した第1の固定部材2付き電解質膜3を準備し、図8に示すように、電解質膜3の上方に第2の固定部材4付きカソード電極5を配置し、電解質膜3の下方に第3の固定部材6付きアノード電極7を配置する。そして、第2及び第3の固定部材4,6の環状凸部42,62を第1の固定部材2の環状凹部22に嵌合させることで、第1の固定部材2に第2及び第3の固定部材4,6を固定する。これにより、電解質膜3、カソード電極5、及びアノード電極7が一体となる。なお、このとき、電解質膜3に各触媒層52,72が接触した状態となっている。   The electrolyte membrane 3 with the first fixing member 2 formed as described above is prepared, and the cathode electrode 5 with the second fixing member 4 is disposed above the electrolyte membrane 3 as shown in FIG. The anode electrode 7 with the third fixing member 6 is disposed below the first electrode. Then, the second and third fixing members 4 and 6 are fitted into the annular recesses 22 of the first fixing member 2 by fitting the annular protrusions 42 and 62 of the second fixing member 4 and 6 to the first fixing member 2. The fixing members 4 and 6 are fixed. Thereby, the electrolyte membrane 3, the cathode electrode 5, and the anode electrode 7 are united. At this time, the catalyst layers 52 and 72 are in contact with the electrolyte membrane 3.

なお、第1の固定部材2と、第2及び第3の固定部材4,6とのシール性を向上させるために、接着剤等を使用して、第2及び第3の固定部材4,6の環状凸部42,62を第1の固定部材2の環状凹部22に接着させてもよい。この場合、環状凹部22の壁面もしくは環状凸部42,62の壁面、またはその両方に接着剤を、公知の塗布方法により塗布すればよく、塗布法としては、刷毛塗り、スプレー、ディスペンサー、インクジェット等が利用できる。また、上記接着に用いる接着剤は公知の接着剤を広く使用することができる。例えば、酢酸ビニールエマルジョン接着剤、ニトリルゴム系接着剤、エポキシ系接着剤、アクリル系接着剤、シアノアクリル系接着剤、塩化ビニール系接着剤、シリコーンゴム系接着剤、ホットボンド・ホットメルト等が利用できる。接着剤を塗布後、環状凹部22と環状凸部42,62を嵌合させ固定する、もしくは接着剤を塗布後に熱プレスにより接着剤を熱溶融させることにより固定する、ことによりシール性を高めることがきる。   In addition, in order to improve the sealing performance between the first fixing member 2 and the second and third fixing members 4, 6, the second and third fixing members 4, 6 are used using an adhesive or the like. The annular protrusions 42 and 62 may be bonded to the annular recess 22 of the first fixing member 2. In this case, an adhesive may be applied to the wall surface of the annular recess 22 or the wall surfaces of the annular protrusions 42 and 62 by using a known coating method. Examples of the coating method include brush coating, spraying, dispenser, and inkjet. Is available. Moreover, the well-known adhesive agent can be widely used for the adhesive agent used for the said adhesion | attachment. For example, vinyl acetate emulsion adhesives, nitrile rubber adhesives, epoxy adhesives, acrylic adhesives, cyanoacrylic adhesives, vinyl chloride adhesives, silicone rubber adhesives, hot bonds and hot melts are used. it can. After applying the adhesive, the annular recess 22 and the annular protrusions 42 and 62 are fitted and fixed, or the adhesive is fixed by hot-melting the adhesive by hot pressing after applying the adhesive, thereby improving the sealing performance. I'm going.

このように作製した固体アルカリ形燃料電池1は、カソード電極5に酸素や空気等の酸化剤ガスを供給し、アノード電極7に水素等の燃料ガス又は液体燃料などを供給することで、発電が行われる。なお、液体燃料としては、例えば、メタノール、エタノール、プロパノールなどの一価アルコール、エチレングリコール、プロピレングリコール等の多価アルコール等のアルコール又はこれらアルコールを混合する水溶液等を挙げることができる。液体燃料の場合は、アルカリ水溶液を添加することができる。アルカリ水溶液を添加する場合は、添加後のpHが通常9〜14程度となるように添加すればよい。このようなアルカリとしては、具体的には、KOH溶液、NaOH溶液等を使用すればよい。また、液体燃料を使用する場合は、図9に示すように、液体燃料をアノード電極7に効率的に供給するために、燃料吸い上げ材8を使用することができる。この燃料吸い上げ材8は、液体燃料内に配置されるとともに燃料吸い上げ材8の上面が第3の固定部材6の下面に接触するように配置される。燃料吸い上げ材8の材質としては、例えば、発泡ウレタン等のスポンジや、発泡ポリプロピレン等の高分子多孔質体が挙げられる。   The solid alkaline fuel cell 1 manufactured in this way supplies power to the cathode electrode 5 by supplying an oxidant gas such as oxygen or air and supplies the anode electrode 7 with a fuel gas such as hydrogen or a liquid fuel. Done. Examples of the liquid fuel include alcohols such as monohydric alcohols such as methanol, ethanol and propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, and aqueous solutions in which these alcohols are mixed. In the case of liquid fuel, an alkaline aqueous solution can be added. What is necessary is just to add so that pH after addition may become about 9-14 normally, when adding aqueous alkali solution. Specifically, as such an alkali, a KOH solution, an NaOH solution, or the like may be used. When liquid fuel is used, as shown in FIG. 9, a fuel wicking material 8 can be used to efficiently supply the liquid fuel to the anode electrode 7. The fuel wicking material 8 is disposed in the liquid fuel, and the upper surface of the fuel wicking material 8 is disposed so as to contact the lower surface of the third fixing member 6. Examples of the material of the fuel sucking material 8 include a sponge such as urethane foam and a polymer porous body such as foamed polypropylene.

以上、本実施形態によれば、各固定部材2,4,6に形成された環状凹部22と環状凸部42,62とを嵌合させることで電解質膜3と各電極5,7とを一体化させるため、各電極5,7の位置精度を向上させることができる。   As described above, according to the present embodiment, the electrolyte membrane 3 and the electrodes 5, 7 are integrated by fitting the annular recess 22 formed in each of the fixing members 2, 4, 6 and the annular projections 42, 62. Therefore, the positional accuracy of the electrodes 5 and 7 can be improved.

以上、本発明の実施形態について説明したが、本発明はこれらに限定されるものではなく、本発明の趣旨を逸脱しない限りにおいて種々の変更が可能である。例えば、図10に示すように、各電極5,7に電気的に接続されるとともに第2及び第3の固定部材4,6を貫通して外部へと延びる集電部9を第2及び第3の固定部材4,6に取り付けることもできる。この集電部9の材質として、好ましくは、アルミニウム、ニッケル、銅、銀、金、白金等を挙げることができる。   As mentioned above, although embodiment of this invention was described, this invention is not limited to these, A various change is possible unless it deviates from the meaning of this invention. For example, as shown in FIG. 10, the current collector 9 is electrically connected to the electrodes 5 and 7 and extends through the second and third fixing members 4 and 6 to the outside. It can also be attached to the three fixing members 4 and 6. Preferred examples of the material for the current collector 9 include aluminum, nickel, copper, silver, gold, and platinum.

また、図11に示すように、電解質膜3の両面に触媒層52,72が形成された膜触媒層接合体10に第1の固定部材2を取り付け、多孔質体51,71のみに第2及び第3の固定部材4,6を取り付けるような構成とすることもできる。   In addition, as shown in FIG. 11, the first fixing member 2 is attached to the membrane / catalyst layer assembly 10 in which the catalyst layers 52 and 72 are formed on both surfaces of the electrolyte membrane 3, and the second material is attached only to the porous bodies 51 and 71. And it can also be set as the structure which attaches the 3rd fixing members 4 and 6. FIG.

また、上記実施形態では、金型内に樹脂を充填させることで電解質膜3へ第1の固定部材2を取り付けていたが、第1の固定部材2の電解質膜3へ取り付ける方法は特にこれに限定されるものではなく、例えば、上下に2分割された第1の固定部材2を用意し、この第1の固定部材2によって電解質膜3を挟んで取り付けることもできる。   Moreover, in the said embodiment, although the 1st fixing member 2 was attached to the electrolyte membrane 3 by filling resin in a metal mold | die, the method of attaching to the electrolyte membrane 3 of the 1st fixing member 2 is especially to this. For example, the first fixing member 2 divided into two parts in the vertical direction can be prepared, and the electrolyte membrane 3 can be sandwiched and attached by the first fixing member 2.

実施例を用いて本発明をさらに詳述する。なお、本発明は下記の実施例に限定されるものではない。   The present invention will be described in further detail using examples. In addition, this invention is not limited to the following Example.

(実施例1)
電解質膜3、カソード電極5、及びアノード電極7に固定部材を成形するための金型を作製した。電極用の金型は、第2及び第3の固定部材が65×65mm、厚さ3.5mmになるように調節した。金型には、電極を過度に潰さないように入れ子構造を設け、電極の厚さを比較的自由に調整できるようにした。
Example 1
A mold for forming a fixing member on the electrolyte membrane 3, the cathode electrode 5, and the anode electrode 7 was produced. The electrode mold was adjusted so that the second and third fixing members were 65 × 65 mm and the thickness was 3.5 mm. The mold was provided with a nested structure so as not to crush the electrode excessively, so that the thickness of the electrode could be adjusted relatively freely.

電解質膜3に形成する第1の固定部材2は、図2に示すような形状であって第2及び第3の固定部材4,6と嵌合できるよう、金型を用いて作製した。   The first fixing member 2 formed on the electrolyte membrane 3 has a shape as shown in FIG. 2 and was manufactured using a mold so that the first fixing member 2 can be fitted to the second and third fixing members 4 and 6.

電解質膜3として65×65mmのアニオン製電解質膜(トクヤマ社製、A−006,厚さ30μm)、カソード電極5の多孔質体51として50×50mmのカーボンクロス(E−TEK社製、LT−1200W、厚さ300μm)、アノード電極7の多孔質体71として、50×50mmの発泡ニッケル(三菱マテリアル社製、厚さ500μm、呼び口径150μm)を用い、それぞれ、射出成形機(住友重工製、SE−100D)に取り付けた上記金型にセットした。   65 × 65 mm anion electrolyte membrane (A-006, thickness 30 μm) as electrolyte membrane 3, 50 × 50 mm carbon cloth (E-TEK, LT-) as porous body 51 of cathode electrode 5 As the porous body 71 of the anode electrode 7, a foamed nickel of 50 × 50 mm (Mitsubishi Materials, thickness 500 μm, nominal diameter 150 μm) is used as an injection molding machine (Sumitomo Heavy Industries, It was set in the above-mentioned mold attached to SE-100D).

各固定部材用の樹脂(ポリプラスチック製、ベクトラ、D408)を熱風乾燥機にて140℃、4時間乾燥させた。そして乾燥した樹脂を上記射出成形機のホッパーに入れ、樹脂を330℃に加熱した。金型の温度が55℃に到達した後、自動移載機(ユーシン精機製)を用いて、4本のゲートが各樹脂導入位置に整合するよう金型内の所定の位置に電解質膜3や各電極5,7を配置した。部材固定用の吸引機構を作動させて金型内の電解質膜3や各電極5,7を固定し、そのまま型締めした。樹脂を250mm/秒の速度で射出し、冷却後、上記自動移載機で固定部材付きの電解質膜3及び各多孔質体51,71を取り出した。   The resin for each fixing member (polyplastic, Vectra, D408) was dried with a hot air dryer at 140 ° C. for 4 hours. The dried resin was placed in the hopper of the injection molding machine, and the resin was heated to 330 ° C. After the temperature of the mold reaches 55 ° C., using an automatic transfer machine (manufactured by Yushin Seiki), the electrolyte membrane 3 or the like is placed at a predetermined position in the mold so that the four gates are aligned with the respective resin introduction positions. Each electrode 5 and 7 was arranged. The suction mechanism for fixing the member was operated to fix the electrolyte membrane 3 and the electrodes 5 and 7 in the mold, and the mold was clamped as it was. The resin was injected at a speed of 250 mm / second, and after cooling, the electrolyte membrane 3 with the fixing member and the porous bodies 51 and 71 were taken out by the automatic transfer machine.

次に、各固定部材が取り付けられた多孔質体51,71に、触媒層52,72を形成した。電解質バインダーとしては、芳香族ポリエーテルスルホン酸と芳香族ポリチオエーテルスルホン酸との共重合体のクロロメチル化物をアミノ化することにより、5wt%アニオン(水酸基イオン)伝導性高分子電解質100gを得た。   Next, catalyst layers 52 and 72 were formed on the porous bodies 51 and 71 to which the respective fixing members were attached. As an electrolyte binder, 100 g of a 5 wt% anion (hydroxyl ion) conductive polymer electrolyte was obtained by amination of a chloromethylated product of a copolymer of aromatic polyether sulfonic acid and aromatic polythioether sulfonic acid. .

アノード電極7用の多孔質体71には、スプレー法によりアノード触媒層72として白金担持カーボン触媒(田中貴金属工業製、TEC10E50E)と水、エタノールからなる触媒分散液を4mg/cmとなるように吹き付け、アノード触媒層72を形成した。 In the porous body 71 for the anode electrode 7, a catalyst dispersion composed of a platinum-supported carbon catalyst (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E), water, and ethanol as an anode catalyst layer 72 by a spray method is 4 mg / cm 2. The anode catalyst layer 72 was formed by spraying.

また、カソード触媒層52として、上記で作製した触媒分散液を4mg/cmとなるように、多孔質体51に吹き付けてカソード触媒層52を形成した。 Moreover, as the cathode catalyst layer 52, the catalyst dispersion liquid produced above was sprayed on the porous body 51 so as to be 4 mg / cm 2 , thereby forming the cathode catalyst layer 52.

以上のように作製した固定部材4,6付きのカソード電極5,アノード電極7を、図8に示すように、触媒層52,72同士が電解質膜3を介して対面するように配置し、層構成がカソード電極5/電解質膜3/アノード電極7となるよう、エポキシ樹脂を用いてプレスしながら一体化し、固体アルカリ形燃料電池1を作製した。   The cathode electrode 5 and the anode electrode 7 with the fixing members 4 and 6 produced as described above are arranged so that the catalyst layers 52 and 72 face each other through the electrolyte membrane 3 as shown in FIG. The solid alkaline fuel cell 1 was manufactured by pressing and integrating with an epoxy resin so that the structure was cathode electrode 5 / electrolyte membrane 3 / anode electrode 7.

(比較例1)
電解質膜3,カソード電極5,アノード電極7の外周縁部のみに凹部や凸部が形成されていない平坦な固定部材を形成し、層構成がカソード電極5/電解質膜3/アノード電極7となるように、エポキシ樹脂を用いてプレスしながら一体化した。
(Comparative Example 1)
A flat fixing member having no concave portion or convex portion is formed only on the outer peripheral edge portion of the electrolyte membrane 3, the cathode electrode 5, and the anode electrode 7, and the layer configuration becomes the cathode electrode 5 / electrolyte membrane 3 / anode electrode 7. Thus, it integrated, pressing using an epoxy resin.

(評価方法)
得られた実施例1の成型品を島津製作所製のマイクロフォーカスX線CT装置(SMX-130CT-SV3)を用いて、X線による透過画像により目視にて位置ズレが無いことを確認した。一方、比較例1は位置ズレがあった。
(Evaluation methods)
The obtained molded product of Example 1 was confirmed by visual observation using a transmission image by X-ray using a microfocus X-ray CT apparatus (SMX-130CT-SV3) manufactured by Shimadzu Corporation. On the other hand, Comparative Example 1 had a positional shift.

1 固体アルカリ形燃料電池
2 第1の固定部材
21 開口部
22 環状凹部(被嵌合部)
3 電解質膜
4 第2の固定部材
41 天板部
42 環状凸部(嵌合部)
43 貫通孔
5 カソード電極
51、71 多孔質体
52、72 触媒層
6 第3の固定部材
61 天板部
62 環状凸部(嵌合部)
63 貫通孔
7 アノード電極
9 集電部
DESCRIPTION OF SYMBOLS 1 Solid alkaline fuel cell 2 1st fixing member 21 Opening part 22 Annular recessed part (fitting part)
3 Electrolyte membrane 4 Second fixing member 41 Top plate portion 42 Annular convex portion (fitting portion)
43 Through-hole 5 Cathode electrode 51, 71 Porous body 52, 72 Catalyst layer 6 Third fixing member 61 Top plate part 62 Annular convex part (fitting part)
63 Through-hole 7 Anode electrode 9 Current collector

Claims (8)

電解質膜と、
前記電解質膜に取り付けられ、被嵌合部を有する第1の固定部材と、
前記電解質膜の一方面上に積層されたカソード電極と、
前記カソード電極に取り付けられ、前記カソード電極を前記電解質膜の一方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第2の固定部材と、
前記電解質膜の他方面上に積層されたアノード電極と、
前記アノード電極に取り付けられ、前記アノード電極を前記電解質膜の他方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第3の固定部材と、
を備えた、固体アルカリ形燃料電池。
An electrolyte membrane;
A first fixing member attached to the electrolyte membrane and having a fitted portion;
A cathode electrode laminated on one surface of the electrolyte membrane;
A second fixing member attached to the cathode electrode and having a fitting portion that fits with a fitted portion of the first fixing member when the cathode electrode is laminated on one surface of the electrolyte membrane;
An anode electrode laminated on the other surface of the electrolyte membrane;
A third fixing member attached to the anode electrode, and having a fitting portion that fits with a fitted portion of the first fixing member when the anode electrode is laminated on the other surface of the electrolyte membrane;
A solid alkaline fuel cell.
前記第1の固定部材は、中央に開口部を有する枠状であって前記電解質膜の外周縁部に取り付けられており、前記被嵌合部として両面に環状凹部が形成されており、
前記第2及び第3の固定部材は、前記嵌合部として前記環状凹部に嵌合する環状凸部が形成されている、請求項1に記載の固体アルカリ形燃料電池。
The first fixing member has a frame shape having an opening at the center and is attached to the outer peripheral edge of the electrolyte membrane, and annular recesses are formed on both surfaces as the fitted portion,
2. The solid alkaline fuel cell according to claim 1, wherein the second and third fixing members are formed with annular convex portions that fit into the annular concave portions as the fitting portions.
前記カソード電極及びアノード電極は、多孔質体と、前記多孔質体の一方面上に形成された触媒層とを有し、前記触媒層が前記電解質膜と接触するように前記電解質膜上に積層され、
前記第2及び第3の固定部材のうち少なくとも一方は、前記カソード電極またはアノード電極よりも一回り大きく形成され前記多孔質体の他方面上に接合した天板部を有しており、前記嵌合部が前記天板部の外周縁部に形成され、
前記天板部は、前記多孔質体の他方面が露出するよう複数の貫通孔が形成されている、請求項1又は2に記載の固体アルカリ形燃料電池。
The cathode electrode and the anode electrode have a porous body and a catalyst layer formed on one surface of the porous body, and are laminated on the electrolyte membrane so that the catalyst layer is in contact with the electrolyte membrane. And
At least one of the second and third fixing members has a top plate portion formed slightly larger than the cathode electrode or the anode electrode and joined to the other surface of the porous body. A joint is formed on the outer peripheral edge of the top plate,
3. The solid alkaline fuel cell according to claim 1, wherein the top plate portion has a plurality of through holes so that the other surface of the porous body is exposed.
前記カソード電極に電気的に接続される第1の集電部と、
前記アノード電極に電気的に接続される第2の集電部と、
をさらに備えた、請求項1〜3のいずれかに記載の固体アルカリ形燃料電池。
A first current collector electrically connected to the cathode electrode;
A second current collector electrically connected to the anode electrode;
The solid alkaline fuel cell according to claim 1, further comprising:
前記第1の固定部材及び第2の固定部材は、互いに嵌合した際に前記カソード電極の側面を気密に覆い、
前記第1の固定部材及び第3の固定部材は、互いに嵌合した際に前記アノード電極の側面を気密に覆う、請求項1〜4のいずれかに記載の固体アルカリ形燃料電池。
The first fixing member and the second fixing member airtightly cover the side surface of the cathode electrode when fitted to each other;
5. The solid alkaline fuel cell according to claim 1, wherein the first fixing member and the third fixing member hermetically cover a side surface of the anode electrode when fitted to each other.
嵌合部を有する固定部材付き電極が積層される、固体アルカリ形燃料電池用の固定部材付き電解質膜であって、
電解質膜と、
前記電解質膜に取り付けられ、固定部材付き電極の嵌合部と嵌合する被嵌合部を有する固定部材と、
を備えた、固定部材付き電解質膜。
An electrolyte membrane with a fixing member for a solid alkaline fuel cell, in which an electrode with a fixing member having a fitting portion is laminated,
An electrolyte membrane;
A fixing member attached to the electrolyte membrane and having a fitted portion that fits with a fitting portion of an electrode with a fixing member;
An electrolyte membrane with a fixing member.
被嵌合部を有する固定部材付き電解質膜に積層される、固体アルカリ形燃料電池用の固定部材付き電極であって、
電極と、
前記電極に取り付けられ、固定部材付き電解質膜の被嵌合部と嵌合する嵌合部を有する固定部材と、
を備えた、固定部材付き電極。
An electrode with a fixing member for a solid alkaline fuel cell, which is laminated on an electrolyte membrane with a fixing member having a fitted portion,
Electrodes,
A fixing member attached to the electrode and having a fitting portion that fits with a fitting portion of an electrolyte membrane with a fixing member;
An electrode with a fixing member.
電解質膜の両面に触媒層が形成された膜触媒層接合体と、
前記膜触媒層接合体に取り付けられ、被嵌合部を有する第1の固定部材と、
前記膜触媒層の一方面上に積層されたカソード電極用の多孔質体と、
前記カソード電極用の多孔質体に取り付けられ、前記カソード電極用の多孔質体を前記膜触媒層接合体の一方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第2の固定部材と、
前記膜触媒層の他方面上に積層されたアノード電極用の多孔質体と、
前記アノード電極用の多孔質体に取り付けられ、前記アノード電極用の多孔質体を前記膜触媒層接合体の他方面上に積層した際に前記第1の固定部材の被嵌合部と嵌合する嵌合部を有する第3の固定部材と、
を備えた、固体アルカリ形燃料電池。
A membrane-catalyst layer assembly in which catalyst layers are formed on both surfaces of the electrolyte membrane;
A first fixing member attached to the membrane catalyst layer assembly and having a fitted portion;
A porous body for a cathode electrode laminated on one surface of the membrane catalyst layer;
The cathode electrode porous body is attached to the cathode electrode porous body, and when the cathode electrode porous body is laminated on one surface of the membrane-catalyst layer assembly, the first fixing member is fitted to the fitted portion. A second fixing member having a fitting portion to be
A porous body for an anode electrode laminated on the other surface of the membrane catalyst layer;
Attached to the anode electrode porous body and fitted with the mating portion of the first fixing member when the anode electrode porous body is laminated on the other surface of the membrane-catalyst layer assembly A third fixing member having a fitting portion to be
A solid alkaline fuel cell.
JP2009032972A 2009-02-16 2009-02-16 Solid alkaline fuel cell, and electrolyte membrane with fixing member and electrode with fixing member for use in the solid alkaline fuel cell Pending JP2010192160A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016525264A (en) * 2013-11-01 2016-08-22 エルジー・ケム・リミテッド Fuel cell and manufacturing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016525264A (en) * 2013-11-01 2016-08-22 エルジー・ケム・リミテッド Fuel cell and manufacturing method thereof

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