TW202013794A - Electrode for fuel cell, fuel cell and method for manufacturing electrode for fuel cell - Google Patents

Electrode for fuel cell, fuel cell and method for manufacturing electrode for fuel cell Download PDF

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TW202013794A
TW202013794A TW108127820A TW108127820A TW202013794A TW 202013794 A TW202013794 A TW 202013794A TW 108127820 A TW108127820 A TW 108127820A TW 108127820 A TW108127820 A TW 108127820A TW 202013794 A TW202013794 A TW 202013794A
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electrode
fuel cell
conductive substrate
oxygen
fuel
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TW108127820A
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岡部晃
佐佐木豊明
井上謙吾
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日商三井化學股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a fuel cell (10) comprising an air electrode (13), a fuel electrode (11), and an electrolyte (12) disposed between the air electrode (13) and the fuel electrode (11). As an example, the air electrode (13) includes an electrically conductive substrate (15), an electrode catalyst, and an oxygen permeable membrane (14), and has a structure in which the electrically conductive substrate (15) and the oxygen permeable membrane (14)are bonded in direct contact with each other. There is an oxygen permeable membrane/electrically conductive substrate mixed layer (145) between the electrically conductive substrate (15) and the oxygen permeable membrane (14).

Description

燃料電池用電極、燃料電池及燃料電池用電極之製造方法 Fuel cell electrode, fuel cell and method for manufacturing fuel cell electrode

本發明係關於燃料電池用電極、燃料電池及燃料電池用電極之製造方法。 The invention relates to a fuel cell electrode, a fuel cell, and a method for manufacturing a fuel cell electrode.

有關微生物燃料電池(Microbial Fuel Cell：MFC)之電極的技術，有專利文獻1及2所記載者。 The technology of the electrode of a microbial fuel cell (MFC) is described in Patent Documents 1 and 2.

於專利文獻1(日本專利特表2015-525692號公報)記載有於MFC中所使用之膜。具體而言，於該文獻中記載使用一種包含具有高透氧性之聚合物之第1層、與由織材料或不織材料所製造之第2支撐層的膜，雙方之層係藉由使用接黏劑而一起點狀積層或圖案狀積層；藉此，可提供尤其可用於MFC領域、經改良之電極構成及與其一起使用之電子-氣體/收集-穿透系統。 Patent Document 1 (Japanese Patent Laid-Open No. 2015-525692) describes a film used in MFC. Specifically, the document describes the use of a film that includes a first layer of a polymer with high oxygen permeability and a second support layer made of a woven material or a nonwoven material. Both layers are used by It is dot-shaped or patterned together with adhesive; thereby, it can provide an electron-gas/collection-penetration system that can be used especially in the field of MFC, improved electrode structure and use with it.

又，專利文獻2(國際專利公開第2015/025917號)中作為用於提供導電性高、耐腐蝕性高且廉價之微生物燃料電池用電極及微生物燃料電池用電極之製造方法的技術，記載有一種用於微生物燃料電池，具備導電性基材、與被覆導電性基材之表面的被膜；被膜係使用導電性碳材料及樹脂所形成，藉由以被膜被覆導電性基材而構成微生物燃料電池用電極，且其電阻率為特定範圍。而且，其記載有此電極係將含有樹脂及有機溶劑之導電性碳材料含有 液塗佈至導電性基材後，使有機溶劑蒸發去除而得者。 In addition, Patent Document 2 (International Patent Publication No. 2015/025917) describes a technique for providing a microbial fuel cell electrode with high conductivity, high corrosion resistance, and low cost, and a method for manufacturing a microbial fuel cell electrode. A microbial fuel cell, comprising a conductive substrate and a coating covering the surface of the conductive substrate; the coating is formed using a conductive carbon material and a resin, and the microbial fuel cell is formed by coating the conductive substrate with a coating An electrode is used, and its resistivity is within a specific range. Furthermore, it is described that this electrode is obtained by applying a conductive carbon material-containing liquid containing a resin and an organic solvent to a conductive substrate and then evaporating and removing the organic solvent.

[先前技術文獻] [Prior Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特表2015-525692號公報 Patent Literature 1: Japanese Patent Special Publication No. 2015-525692

專利文獻2：國際專利公開第2015/025917號 Patent Literature 2: International Patent Publication No. 2015/025917

本案發明人等針對以微生物燃料電池為首之具備電解液之燃料電池的空氣電極進行了檢討，結果發現，在依簡便構造得到高輸出之方面尚有改善空間。 The inventors of the present application reviewed the air electrode of a fuel cell equipped with an electrolyte, including a microbial fuel cell, and found that there is room for improvement in achieving high output with a simple structure.

因此，本發明係提供可用於具備電解液之燃料電池之空氣電極、可依簡便構造獲得高輸出的電極。 Therefore, the present invention provides an electrode that can be used for an air electrode of a fuel cell equipped with an electrolyte and can obtain a high output with a simple structure.

根據本發明，提供以下所示燃料電池用電極、燃料電池及燃料電池用電極之製造方法。 According to the present invention, there are provided fuel cell electrodes, fuel cells, and methods for manufacturing fuel cell electrodes shown below.

[1]一種燃料電池用電極，係使用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中的電極； [1] An electrode for a fuel cell, which is an electrode used in a fuel cell including an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode;

上述空氣電極係包含導電性基材、電極觸媒及透氧膜，並為： The air electrode system includes a conductive substrate, an electrode catalyst, and an oxygen-permeable membrane, and is:

(A)透氧膜層 (A) Oxygen permeable membrane

(AB)透氧膜‧導電性基材混合層 (AB) Oxygen permeable membrane and conductive substrate mixed layer

(B)導電性基材層 (B) Conductive substrate layer

(C)電極觸媒層 之順序的積層構造； (C) The layered structure of the electrode catalyst layer in order;

上述(A)層為熱可塑性樹脂層，上述(A)層之厚度為0.1μm以上且280μm以下。 The (A) layer is a thermoplastic resin layer, and the thickness of the (A) layer is 0.1 μm or more and 280 μm or less.

[2]一種燃料電池用電極，係使用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中的電極； [2] An electrode for a fuel cell, which is an electrode used in a fuel cell provided with an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode;

其包含導電性基材、電極觸媒及透氧膜， It contains conductive substrate, electrode catalyst and oxygen permeable membrane,

上述導電性基材與上述透氧膜直接相接並壓黏。 The conductive substrate is directly in contact with the oxygen-permeable membrane and is pressure-bonded.

[3]如[2]之燃料電池用電極，其中，上述透氧膜之膜厚為0.1μm以上且1000μm以下。 [3] The fuel cell electrode according to [2], wherein the film thickness of the oxygen permeable membrane is 0.1 μm or more and 1000 μm or less.

[4]如[1]或[2]之燃料電池用電極，其中，上述空氣電極之上述導電性基材之材料為碳材料。 [4] The fuel cell electrode according to [1] or [2], wherein the material of the conductive substrate of the air electrode is a carbon material.

[5]如[2]之燃料電池用電極，其中，上述透氧膜係包含熱可塑性樹脂。 [5] The fuel cell electrode according to [2], wherein the oxygen-permeable membrane contains a thermoplastic resin.

[6]如[1]或[5]之燃料電池用電極，其中，上述透氧膜係包含熱可塑性樹脂，該熱可塑性樹脂由示差掃描熱量測定裝置所決定之融點及玻璃轉移溫度之至少一者為100~300℃之範圍。 [6] The fuel cell electrode according to [1] or [5], wherein the oxygen permeable membrane includes a thermoplastic resin having at least a melting point and a glass transition temperature determined by a differential scanning calorimeter One is in the range of 100~300℃.

[7]如[1]或[5]之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材料係包含選自由聚4-甲基-1-戊烯、聚丁烯、聚四氟乙烯、聚二甲基矽氧烷所構成群之任一種樹脂。 [7] The fuel cell electrode according to [1] or [5], wherein the material of the oxygen permeable membrane of the air electrode is selected from the group consisting of poly-4-methyl-1-pentene, polybutene, and polytetramethylene Any one of the resins composed of vinyl fluoride and polydimethylsiloxane.

[8]如[1]或[5]之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材料係包含聚4-甲基-1-戊烯。 [8] The fuel cell electrode according to [1] or [5], wherein the material of the oxygen permeable membrane of the air electrode includes poly 4-methyl-1-pentene.

[9]如[1]或[2]之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含選自由Ru、Rh、Ir、Ni、Pd、Pt、Cu、Ag 及Au所構成群之1種或2種以上金屬。 [9] The fuel cell electrode according to [1] or [2], wherein the material of the electrode catalyst of the air electrode includes a material selected from the group consisting of Ru, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au One or more metals in the group.

[10]如[9]之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含Pt。 [10] The fuel cell electrode according to [9], wherein the material of the electrode catalyst of the air electrode contains Pt.

[11]如[10]之燃料電池用電極，其中，上述空氣電極中，於上述導電性基材之表面設有包含Pt之上述電極觸媒之層。 [11] The fuel cell electrode according to [10], wherein the air electrode is provided with a layer of the electrode catalyst containing Pt on the surface of the conductive substrate.

[12]如[1]或[2]之燃料電池用電極，其中，上述燃料電極係包含可定著發電菌之導電性基材。 [12] The fuel cell electrode according to [1] or [2], wherein the fuel electrode system includes a conductive substrate capable of fixing power generating bacteria.

[13]如[12]之燃料電池用電極，其中，上述燃料電極係包含導電性基材、及作為電極觸媒之發電菌。 [13] The fuel cell electrode according to [12], wherein the fuel electrode system includes a conductive base material and a power generating bacterium as an electrode catalyst.

[14]如[12]之燃料電池用電極，其中，上述燃料電極係包含由碳材料所構成之導電性基材。 [14] The fuel cell electrode according to [12], wherein the fuel electrode includes a conductive base material composed of a carbon material.

[15]如[1]、[2]及[12]中任一項之燃料電池用電極，其中，上述燃料電池係以家畜***物作為燃料。 [15] The fuel cell electrode according to any one of [1], [2], and [12], wherein the fuel cell uses livestock excrement as fuel.

[16]一種燃料電池，係具備[1]、[2]、[12]及[15]中任一項之燃料電池用電極。 [16] A fuel cell comprising the fuel cell electrode of any one of [1], [2], [12], and [15].

[17]如[16]之燃料電池，其不包含質子傳導膜作為構成要件。 [17] The fuel cell according to [16], which does not contain a proton conductive membrane as a constituent element.

[18]一種燃料電池用電極之製造方法，係用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池之空氣電極的電極之製造方法；其包含： [18] A method of manufacturing a fuel cell electrode, which is a method of manufacturing an electrode for an air electrode of a fuel cell including an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode; Contains:

藉由導電性基材與透氧膜依直接相接之狀態進行壓黏，而將上述導電性基材與上述透氧膜接黏的步驟；與 The step of bonding the conductive substrate to the oxygen permeable film by pressure bonding the conductive substrate and the oxygen permeable film in a state of direct contact; and

將電極觸媒固定化於上述導電性基材的步驟。 The step of fixing the electrode catalyst to the conductive substrate.

[19]如[18]之燃料電池用電極之製造方法，其中，將電極觸媒固定化於導電性基材之上述步驟，係包含：於上述導電性基材之表 面，藉由濺鍍法或電極還原法，形成含有Pt之上述電極觸媒之層的步驟。 [19] The method for manufacturing an electrode for a fuel cell according to [18], wherein the step of fixing the electrode catalyst to the conductive substrate includes: on the surface of the conductive substrate by a sputtering method Or electrode reduction method, the step of forming a layer of the above-mentioned electrode catalyst containing Pt.

[20]如[19]之燃料電池用電極之製造方法，其中，形成電極觸媒之層的上述步驟，係藉由上述濺鍍法形成含有Pt之上述層的步驟。 [20] The method for manufacturing a fuel cell electrode according to [19], wherein the step of forming the electrode catalyst layer is a step of forming the Pt-containing layer by the sputtering method.

根據本發明，可提供能使用於具備電解液之燃料電池的空氣電極，並可依簡便構造獲得高輸出的電極。 According to the present invention, it is possible to provide an electrode that can be used in an air electrode of a fuel cell equipped with an electrolyte and can obtain a high output according to a simple structure.

10‧‧‧燃料電池 10‧‧‧ fuel cell

11‧‧‧燃料電極 11‧‧‧ Fuel electrode

12‧‧‧電解液 12‧‧‧Electrolyte

13‧‧‧空氣電極 13‧‧‧Air electrode

14‧‧‧透氧膜 14‧‧‧Oxygen permeable membrane

15‧‧‧導電性基材 15‧‧‧ conductive substrate

16‧‧‧大氣 16‧‧‧Atmosphere

17‧‧‧外部電阻 17‧‧‧External resistance

18‧‧‧容器 18‧‧‧Container

19‧‧‧電極觸媒層 19‧‧‧electrode catalyst layer

21a‧‧‧加熱板 21a‧‧‧Heating plate

21b‧‧‧加熱板 21b‧‧‧Heating plate

145‧‧‧透氧膜‧導電性基材混合層 145‧‧‧Oxygen permeable membrane‧ mixed layer of conductive substrate

圖1係概略表示實施形態之燃料電池之構成例的剖面圖。 FIG. 1 is a cross-sectional view schematically showing a configuration example of a fuel cell of an embodiment.

圖2(a)及(b)係概略表示實施形態之燃料電池用電極之構成例的剖面圖。 2(a) and (b) are cross-sectional views schematically showing a configuration example of the fuel cell electrode of the embodiment.

圖3(a)及(b)係說明實施形態之燃料電池用電極之製造方法例的剖面圖。 3(a) and (b) are cross-sectional views illustrating an example of a method of manufacturing a fuel cell electrode according to an embodiment.

圖4係表示實施形態之空氣電極之剖面構造一例的圖。 4 is a diagram showing an example of a cross-sectional structure of an air electrode according to an embodiment.

以下使用圖式說明本發明實施形態。又，所有圖式中，對相同構成要件係加註共通符號，並適當省略說明。又，圖為概略圖，與實際尺寸比率並不一致。又，表示數值範圍之「α~β」係在未特別限定之下，表示α以上且β以下。 The embodiments of the present invention will be described below using drawings. In all drawings, common symbols are added to the same constituent elements, and explanations are omitted as appropriate. In addition, the figure is a schematic diagram and does not match the actual size ratio. In addition, “α to β” indicating a numerical range is not particularly limited, and means α or more and β or less.

圖1係概略表示本實施形態之燃料電池之構造一例的剖面圖。將對應至本實施形態之燃料電池之基本構成示於圖1。 FIG. 1 is a cross-sectional view schematically showing an example of the structure of the fuel cell of this embodiment. The basic structure of the fuel cell corresponding to this embodiment is shown in FIG. 1.

圖1中，燃料電池10係具備空氣電極13、燃料電極11、及配 置於空氣電極13與燃料電極11之間之電解液12。本實施形態之特徵在於其電極構造。亦即，用於此種燃料電池10之空氣電極13的電極，係包含(B)導電性基材15、電極觸媒(圖2(a)及圖2(b)之(C)電極觸媒層19)及(A)透氧膜14；如圖2(b)所示亦具有(A)透氧膜14與(B)導電性基材15混合存在之(AB)透氧膜‧導電性基材混合層145。 In FIG. 1, the fuel cell 10 includes an air electrode 13, a fuel electrode 11, and an electrolyte 12 disposed between the air electrode 13 and the fuel electrode 11. This embodiment is characterized by its electrode structure. That is, the electrode used for the air electrode 13 of this fuel cell 10 includes (B) a conductive substrate 15, an electrode catalyst (FIG. 2(a) and FIG. 2(b)(C) electrode catalyst Layer 19) and (A) oxygen-permeable membrane 14; as shown in FIG. 2(b), there are also (AB) oxygen-permeable membranes where (A) oxygen-permeable membrane 14 and (B) conductive substrate 15 are mixed Base material mixed layer 145.

本實施形態中，(AB)透氧膜‧導電性基材混合層145之厚度係在將(B)導電性基材15與(AB)透氧膜‧導電性基材混合層145之厚度合計為100%時，較佳為0.1~60%。更佳下限值為0.3%以上、再更佳為0.5%以上、又更佳為0.7%上、又再更佳為0.8%以上。另一方面，更佳上限值為50%以下、再更佳為45%以下、又更佳為40%以下。 In this embodiment, the thickness of the (AB) oxygen-permeable film ‧ conductive substrate mixed layer 145 is the total thickness of the (B) conductive substrate 15 and the (AB) oxygen-permeable film ‧ conductive substrate mixed layer 145 When it is 100%, it is preferably 0.1 to 60%. The lower limit is more preferably 0.3% or more, even more preferably 0.5% or more, yet more preferably 0.7% or more, and still more preferably 0.8% or more. On the other hand, the more preferable upper limit value is 50% or less, still more preferably 45% or less, and still more preferably 40% or less.

本實施形態之空氣電極13，具體而言係具有圖2(b)所示積層構造。圖2(b)中，設有(A)透氧膜14之材料與(B)導電性基材15之材料混合存在的(AB)透氧膜‧導電性基材混合層145。圖2(b)所示積層構造係例如圖2(a)所示般，藉由依序積層(A)透氧膜14、(B)導電性基材15及(C)電極觸媒層19，並將(A)透氧膜14與(B)導電性基材15壓黏而獲得。獲得空氣電極13之方法之細節將於後述。 Specifically, the air electrode 13 of this embodiment has a laminated structure shown in FIG. 2(b). In FIG. 2(b), the (AB) oxygen permeable film and conductive substrate mixed layer 145 in which (A) the material of the oxygen permeable film 14 and (B) the material of the conductive substrate 15 are mixed are provided. The layered structure shown in FIG. 2(b) is, for example, as shown in FIG. 2(a), by sequentially laminating (A) an oxygen-permeable film 14, (B) a conductive substrate 15, and (C) an electrode catalyst layer 19, The (A) oxygen-permeable membrane 14 and the (B) conductive substrate 15 are obtained by pressure bonding. The details of the method of obtaining the air electrode 13 will be described later.

本實施形態之空氣電極13中，(AB)透氧膜‧導電性基材混合層145較佳係具有密集構造、空隙少。具體而言，(AB)透氧膜‧導電性基材混合層145可藉由將電極剖面擴大為縱橫分別數μm~10μm之比例的掃描型電子顯微鏡照片進行觀察。又，為了製作進行上述剖面觀察之試料，係對上述電極藉由形狀保持用之樹脂等材料(有時稱為包埋材料或包埋樹脂)固定後、較佳係藉由塗佈於 (C)電極觸媒層19側等方法固定後，再切削電極。其他可藉由公知方法作成剖面觀察用資料。 In the air electrode 13 of the present embodiment, the (AB) oxygen-permeable film and conductive base material mixed layer 145 preferably have a dense structure and few voids. Specifically, the (AB) oxygen-permeable film and the conductive base material mixed layer 145 can be observed by scanning electron microscope photographs that enlarge the electrode cross-section to a ratio of several μm to 10 μm in the vertical and horizontal directions. In addition, in order to prepare the sample for the above cross-sectional observation, the electrode is fixed by a material such as a resin for shape retention (sometimes referred to as an embedding material or embedding resin), preferably by coating on (C ) After fixing the electrode catalyst layer 19 side, etc., cut the electrode. Other data for profile observation can be prepared by a known method.

圖4為表示空氣電極13之剖面構造一例的圖。圖4中，作為空氣電極13之構成例，係作成Pt/碳紙/透氧膜(TPX(註冊商標，以下亦同)膜：三井化學公司製)之積層體，並表示藉由掃描型電子顯微鏡(SEM)觀察其剖面的結果。圖4之例中，可知在屬於(B)導電性基材15之碳紙與屬於(A)透氧膜14之TPX膜之混合區域中，碳纖維間幾乎100%被TPX所佔有。亦即，幾乎無空隙。 FIG. 4 is a diagram showing an example of the cross-sectional structure of the air electrode 13. In FIG. 4, as a configuration example of the air electrode 13, a laminate of a Pt/carbon paper/oxygen permeable film (TPX (registered trademark, the same applies hereinafter) film: manufactured by Mitsui Chemicals Co., Ltd.) is shown and shown by the scanning electron The result of observing the cross section with a microscope (SEM). In the example of FIG. 4, it can be seen that almost 100% of the carbon fibers are occupied by TPX in the mixed area of the carbon paper belonging to (B) conductive substrate 15 and the TPX membrane belonging to (A) oxygen permeable membrane 14. That is, there are almost no voids.

此(AB)透氧膜‧導電性基材混合層145中之(B)導電性基材15、與構成(A)透氧膜14之樹脂，較佳係呈可藉由如後述之壓黏方法而實現的混合狀態。 The (AB) oxygen-permeable film and the conductive substrate mixed layer 145 of (B) the conductive substrate 15 and the resin constituting the (A) oxygen-permeable film 14 are preferably such that they can be bonded by pressure as described below Method to achieve a mixed state.

本實施形態之(AB)透氧膜‧導電性基材混合層145之較佳態樣可設定如下述般。 The preferred aspect of the (AB) oxygen-permeable film and conductive substrate mixed layer 145 of this embodiment can be set as follows.

本實施形態之(AB)透氧膜‧導電性基材混合層145係藉由觀察本實施形態之空氣電極13之剖面，可把握其構成。具體而言，對本實施形態之空氣電極13，將依常法進行切削所得之剖面進行電子顯微鏡觀察。於上述切削加工時，視狀況亦可藉由使公知之形狀保持用之樹脂或碳膜等成分附著於空氣電極13之表面部等方法，事先補強空氣電極13。 The (AB) oxygen-permeable membrane and conductive substrate mixed layer 145 of this embodiment can be grasped by observing the cross section of the air electrode 13 of this embodiment. Specifically, for the air electrode 13 of the present embodiment, the cross-section obtained by cutting according to the usual method is observed with an electron microscope. During the cutting process described above, depending on the situation, the air electrode 13 may be reinforced in advance by attaching a well-known shape-preserving resin or carbon film to the surface of the air electrode 13.

本實施形態之(AB)透氧膜‧導電性基材混合層145係於擴大成縱＊橫分別數μm~10μm之比例的本實施形態之空氣電極剖面之掃描型電子顯微鏡照片(使用日立製作所公司製，S-4800型掃描電子顯微鏡)中，較佳係具有包含下述區域的態樣：相鄰之例如10個以上、較佳為20個以上、更佳為30個以上之(B)導電性基材15成分 (例如碳纖維)之間隙的較佳為80面積%以上、更佳為90面積%以上、再更佳為95面積%以上存在(A)透氧膜14之成分的區域。上述所謂相鄰之間隙，係指例如於圖4中，10根以上之碳纖維間(例如縱＊橫為3根＊4根之區域)的間隙。圖4之態樣可如以下般記述。於圖4可見到上述10根以上之碳纖維間幾乎所有均存在TPX之態樣的區域。因此，圖4之態樣係成為於(B)導電性基材15之間隙之約100面積%中存在(A)透氧膜14之成分的態樣。 Forms of the present embodiment (AB) permeable membrane ‧ conductive substrate 145 based on the mixed layer is expanded into a number of horizontal * vertical μm, respectively, scanning electron microscope photograph of this embodiment - an air ratio of the aspect of 10μm cross-sectional view of an electrode (manufactured by Hitachi, Ltd. (S-4800 Scanning Electron Microscope manufactured by the company), preferably including the following areas: adjacent ones such as 10 or more, preferably 20 or more, more preferably 30 or more (B) The gap of the component (for example, carbon fiber) of the conductive substrate 15 is preferably 80 area% or more, more preferably 90 area% or more, and even more preferably 95 area% or more, where the (A) oxygen permeable membrane 14 component exists. The above-mentioned adjacent gap refers to, for example, in FIG. 4, a gap between more than 10 carbon fibers (for example, a region of 3 * 4 in the vertical * horizontal direction). The state of FIG. 4 can be described as follows. In FIG. 4, it can be seen that almost all of the above 10 carbon fibers have TPX-like regions. Therefore, the aspect of FIG. 4 is such that the component of (A) the oxygen-permeable film 14 is present in (B) about 100% of the gap of the conductive substrate 15.

可認為藉由滿足上述條件，可有效地將自外部攝取之空氣(氧)供給至電極觸媒，且維持穩定之積層構造。因此，本案發明人等認為，使用本實施形態之電極的燃料電池可實現高輸出。 It is considered that by satisfying the above conditions, air (oxygen) taken in from the outside can be efficiently supplied to the electrode catalyst, and a stable laminated structure can be maintained. Therefore, the present inventors believe that the fuel cell using the electrode of the present embodiment can achieve high output.

(AB)透氧膜‧導電性基材混合層145係呈例如(B)導電性基材15與(A)透氧膜14直接相接並壓黏的形態。藉由此種壓黏步驟所得的(AB)透氧膜‧導電性基材混合層145，可藉由後述般之壓製法或多層擠出法而實現。 (AB) Oxygen permeable film and conductive substrate mixed layer 145 are in the form of, for example, (B) conductive substrate 15 and (A) oxygen permeable film 14 directly contacted and pressure-bonded. The (AB) oxygen-permeable film and conductive substrate mixed layer 145 obtained by this pressure bonding step can be realized by a pressing method or a multilayer extrusion method as described later.

使用了包含本實施形態之空氣電極之電極的燃料電池，係表示高輸出。可認為相較於藉由習知之接黏材的接黏法或塗裝法，由於可使(B)導電性基材15與(A)透氧膜14依較薄之(A)透氧膜14之狀態、較佳係密集且牢固地接觸之狀態形成，故有助於實現效率佳、較高之輸出。 A fuel cell using an electrode including the air electrode of this embodiment indicates high output. It can be considered that compared with the conventional bonding method or coating method of bonding materials, (B) the conductive substrate 15 and (A) the oxygen permeable film 14 can be thinner than the (A) oxygen permeable film The state of 14 is preferably formed in a densely and firmly contacted state, so it helps to achieve high efficiency and high output.

又，圖1中，燃料電極11與空氣電極13係藉由包含外部電阻17之外部電路所連接。 In FIG. 1, the fuel electrode 11 and the air electrode 13 are connected by an external circuit including an external resistor 17.

又，燃料電極11及空氣電極13係收容於容器18中，且空氣電極13之(A)透氧膜14係構成容器18之外壁的一部分；於(A)透氧膜14之與(B)導電性基材15間之接觸面相反側的面，成為空氣電 極13與大氣16相接的構成。 In addition, the fuel electrode 11 and the air electrode 13 are housed in the container 18, and the (A) oxygen permeable membrane 14 of the air electrode 13 constitutes a part of the outer wall of the container 18; the (A) oxygen permeable membrane 14 and (B) The surface on the opposite side of the contact surface between the conductive base materials 15 has a configuration in which the air electrode 13 is in contact with the atmosphere 16.

電解液12在例如為MFC的情況，係含有成為燃料之有機物，較佳為燃料有機物之水懸浮液。 When the electrolyte 12 is, for example, an MFC, it contains an organic substance that becomes a fuel, preferably an aqueous suspension of fuel organic substance.

於MFC之情況，作為燃料有機物之水懸浮液之具體例，可舉例如包含家畜***物之家畜農家的廢水或家庭廢水等。又，電解液12中亦可添加用於促進發電的添加物，添加物並無特別限制，可舉例如氧化鐵或氫氧化鐵等鐵化合物類。當然，若為MFC以外之狀態，亦可併用習知之使氫(包括將烴改質而得之氫)溶解或起泡之態樣的液體。 In the case of MFC, as a specific example of the aqueous suspension of fuel organic matter, for example, wastewater from livestock farms or domestic wastewater containing livestock excreta can be cited. In addition, an additive for promoting power generation may be added to the electrolytic solution 12, and the additive is not particularly limited, and examples thereof include iron compounds such as iron oxide and iron hydroxide. Of course, if it is in a state other than MFC, it is also possible to use conventionally known liquids in which hydrogen (including hydrogen obtained by upgrading hydrocarbons) is dissolved or foamed.

又，燃料電池10較佳係不含有質子傳導膜作為構成要件。 In addition, the fuel cell 10 preferably does not contain a proton conductive membrane as a constituent element.

於如此構成之燃料電池10中，對燃料電極11供給電解液12中之燃料、具體而言為供給有機物，有機物分解而在產生氫離子之同時釋出電子。 In the fuel cell 10 configured in this manner, the fuel in the electrolytic solution 12 is supplied to the fuel electrode 11, specifically, the organic matter is supplied, and the organic matter is decomposed to release electrons while generating hydrogen ions.

於燃料電極11所產生之氫離子係於電解液12中移動並到達空氣電極13。由燃料電極11釋出之電子係通過外部電路而移動至空氣電極13。對空氣電極13係供給大氣16、即(包含氧)空氣。然後，於空氣電極13中，由氫離子及空氣中之氧生成水。 The hydrogen ions generated in the fuel electrode 11 move in the electrolyte 12 and reach the air electrode 13. The electrons released from the fuel electrode 11 move to the air electrode 13 through an external circuit. The air electrode 13 is supplied with atmospheric air 16, that is, (with oxygen) air. Then, in the air electrode 13, water is generated from hydrogen ions and oxygen in the air.

由以上結果，於外部電路係由燃料電極11朝空氣電極13流動電子，而取出電力。 As a result of this, electrons flow from the fuel electrode 11 toward the air electrode 13 in the external circuit to extract power.

燃料電池10係例如微生物燃料電池。以下，以燃料電池10為微生物燃料電池之情況為例進行說明。 The fuel cell 10 is, for example, a microbial fuel cell. Hereinafter, the case where the fuel cell 10 is a microbial fuel cell will be described as an example.

屬於微生燃料電池之燃料電池10，係以例如家畜***物或食品廢棄物作為燃料。又，作為電解液12，可舉例如家畜***物等含有有機物之廢水、污泥、其他生質懸浮液等。又，作為電 解液12，亦可舉例如將農場所產生之收穫後之葉或莖等經堆肥化後，將其一部分或全部溶解或懸浮於水之態樣。又，電解液12較佳係含有發電菌者。 The fuel cell 10, which is a microbial fuel cell, uses, for example, livestock waste or food waste as fuel. In addition, as the electrolytic solution 12, for example, waste water containing organic matter such as livestock excreta, sludge, other biomass suspensions, and the like can be mentioned. The electrolytic solution 12 may be, for example, a composted leaf or stem produced on a farm, and then a part or all of it may be dissolved or suspended in water. In addition, the electrolytic solution 12 preferably contains power generating bacteria.

然後，於燃料電極11中，藉微生物作用由有機物產生氫離子及電子。具體而言，燃料電極11係含有導電性基材與載持於導電性基材之微生物，較佳係含有導電性基材及作為電極觸媒之發電菌。作為發電菌，可舉例如具有細胞外電子傳達機構的細菌。 Then, in the fuel electrode 11, hydrogen ions and electrons are generated from organic matter by the action of microorganisms. Specifically, the fuel electrode 11 contains a conductive substrate and microorganisms supported on the conductive substrate, and preferably contains a conductive substrate and a power-generating bacterium as an electrode catalyst. Examples of the power generating bacteria include bacteria having an extracellular electron transmission mechanism.

又，微生物若為將燃料所含有機物進行氧化而生成電子者即可，可為1種或2種以上之任意者。作為微生物之具體例，可舉例如希瓦氏菌(Shewanella)屬、地桿菌(Geobacter)屬、地髮菌(Geothrix)屬、氣單胞菌(Aeromonas)屬者。可添加所需微生物使其載持於導電性基材，亦可利用廢水中所含微生物而使其載持。關於微生物之載持方法並無限制，可舉例如使用未載持微生物之導電性基材作為燃料電極11與含有微生物之電解液開始發電，隨著發電使微生物附著於導電性基材的方法等。 In addition, the microorganisms may be any one or two or more if they oxidize organic substances contained in the fuel to generate electrons. Specific examples of microorganisms include those belonging to the genus Shewanella, Geobacter, Geothrix, and Aeromonas. The required microorganisms can be added to be supported on the conductive substrate, and can also be supported by the microorganisms contained in the wastewater. The method for supporting microorganisms is not limited, and examples include a method of using a conductive substrate that does not support microorganisms as the fuel electrode 11 and an electrolyte containing microorganisms to start power generation, and attaching microorganisms to the conductive substrate with power generation, etc. .

由使燃料電極11之反應效率佳地發生的觀點而言，燃料電極11之導電性基材較佳係由發電菌可定著之導電性材料所構成。 From the viewpoint of allowing the reaction efficiency of the fuel electrode 11 to occur efficiently, the conductive substrate of the fuel electrode 11 is preferably composed of a conductive material that can be fixed by the power generating bacteria.

作為導電性材料之具體例可舉例如碳、導電性之金屬。 Specific examples of the conductive material include carbon and conductive metals.

又，由作成為可載持發電菌、同時燃料可於導電性基材內移動之形狀的觀點而言，作為導電性基材，可舉例如氈、織布、不織布、網狀體、燒結體、發泡體等之多孔質基材。由同樣的觀點而言，燃料電極11較佳係包含由碳布、碳紙、碳氈等碳材料或不鏽鋼等金屬材料所構成之導電性基材，其中更佳為碳材料。又，燃料電極11 之導電性基材亦可經表面處理。 In addition, from the viewpoint of forming a shape that can support power generating bacteria and at the same time the fuel can move in the conductive substrate, examples of the conductive substrate include felt, woven fabric, non-woven fabric, mesh body, and sintered body , Foam and other porous substrates. From the same viewpoint, the fuel electrode 11 preferably includes a conductive base material composed of a carbon material such as carbon cloth, carbon paper, carbon felt, or a metal material such as stainless steel, and more preferably a carbon material. In addition, the conductive substrate of the fuel electrode 11 may be surface-treated.

燃料電極11為片材狀時，燃料電極11之厚度係由穩定載持發電菌的觀點而言，較佳為0.1mm以上、更佳為1mm以上。又，由燃料電極11之小型化的觀點而言，燃料電極11之厚度較佳為20mm以下、更佳為10mm以下。 When the fuel electrode 11 is in the form of a sheet, the thickness of the fuel electrode 11 is preferably 0.1 mm or more, and more preferably 1 mm or more from the viewpoint of stably supporting the power generating bacteria. From the viewpoint of miniaturization of the fuel electrode 11, the thickness of the fuel electrode 11 is preferably 20 mm or less, and more preferably 10 mm or less.

於此，燃料電極11之厚度亦可為燃料電極11之導電性基材之厚度。 Here, the thickness of the fuel electrode 11 may also be the thickness of the conductive substrate of the fuel electrode 11.

接著，進一步說明空氣電極13。 Next, the air electrode 13 will be further described.

本實施形態中，空氣電極13較佳係具有(A)透氧膜14、(AB)透氧膜‧導電性基材混合層145、(B)導電性基材15、(C)電極觸媒層19之順序的積層構造。較佳係(AB)透氧膜‧導電性基材混合層145之厚度為特定範圍。如上述，(AB)透氧膜‧導電性基材混合層145較佳係(A)透氧膜14之材料(樹脂)與(B)導電性基材15密集地存在。 In this embodiment, the air electrode 13 preferably has (A) an oxygen-permeable membrane 14, (AB) an oxygen-permeable membrane, a conductive substrate mixed layer 145, (B) a conductive substrate 15, and (C) an electrode catalyst The layered structure in the order of layer 19. It is preferable that the thickness of the (AB) oxygen-permeable film and conductive substrate mixed layer 145 is within a specific range. As described above, the (AB) oxygen-permeable film and conductive substrate mixed layer 145 are preferably such that (A) the material (resin) of the oxygen-permeable film 14 and (B) the conductive substrate 15 are densely present.

空氣電極13中，如上述，以(B)導電性基材15與(A)透氧膜14直接相接並壓黏為較佳態樣。更具體而言，以(B)導電性基材15及(A)透氧膜14不使用接黏劑而壓黏接合為較佳態樣。又，空氣電極13較佳係於(B)導電性基材15與(A)透氧膜14之間不具有上述透氧膜‧導電性基材混合層145、導電性基材15及透氧膜14以外的層(介存層)。 In the air electrode 13, as described above, (B) the conductive substrate 15 and (A) the oxygen-permeable film 14 are directly connected and pressure-bonded is a preferable aspect. More specifically, (B) the conductive substrate 15 and (A) the oxygen-permeable membrane 14 are preferably bonded by pressure bonding without using an adhesive. In addition, the air electrode 13 is preferably provided between the (B) conductive substrate 15 and the (A) oxygen-permeable membrane 14 without the above-mentioned oxygen-permeable film, conductive substrate mixed layer 145, conductive substrate 15 and oxygen-permeable A layer (intermediate layer) other than the film 14.

本實施形態之(A)透氧膜14較佳係含有熱可塑性樹脂，更佳係熱可塑性樹脂之膜。(A)透氧膜14較佳係由透氧性優越、且可抑制電解液12對大氣16之滲漏的材料所構成。如後述，(A)透氧膜14較佳係不使電解液12通過。由此點而言，(A)透氧膜14 之材料為例如具有透氧性之樹脂。(A)透氧膜14較佳係由示差掃描熱量測定裝置所決定之融點及玻璃轉移溫度之至少一者為100~300℃之範圍。又，具有透氧性之樹脂較佳為熱可塑性樹脂，但即使熔融流動性低，若為例如後述可應用壓製成型等之材料則亦可採用。 The (A) oxygen-permeable membrane 14 of the present embodiment preferably contains a thermoplastic resin, and more preferably a thermoplastic resin film. (A) The oxygen-permeable membrane 14 is preferably made of a material that has excellent oxygen permeability and can suppress leakage of the electrolyte 12 into the atmosphere 16. As described later, (A) the oxygen-permeable membrane 14 preferably does not allow the electrolyte 12 to pass through. From this point of view, the material of (A) the oxygen-permeable membrane 14 is, for example, a resin having oxygen permeability. (A) The oxygen-permeable film 14 is preferably at least one of the melting point and the glass transition temperature determined by a differential scanning calorimeter, in the range of 100 to 300°C. In addition, the resin having oxygen permeability is preferably a thermoplastic resin, but even if the melt fluidity is low, it can be used if it is a material that can be applied to press molding, for example, which will be described later.

上述融點之較佳下限值為110℃以上、更佳為120℃以上。另一方面，其上限值為290℃以下、更佳為280℃以下、再更佳為270℃以下。 The preferable lower limit of the melting point is 110°C or higher, and more preferably 120°C or higher. On the other hand, the upper limit is 290°C or lower, more preferably 280°C or lower, and even more preferably 270°C or lower.

又，關於上述玻璃轉移溫度，較佳下限值為110℃以上、更佳為120℃以上。另一方面，其上限值為290℃以下、更佳為280℃以下、再更佳為270℃以下。 In addition, with respect to the glass transition temperature, the lower limit is preferably 110° C. or higher, and more preferably 120° C. or higher. On the other hand, the upper limit is 290°C or lower, more preferably 280°C or lower, and even more preferably 270°C or lower.

又，具有透氧性之樹脂之軟化溫度之上限值較佳為290℃以下、更佳為280℃以下、再更佳為270℃以下。又，本實施形態所使用之(A)透氧膜14之材料(樹脂)較佳係對電解液呈不溶性。例如，在電解液為水系時，較佳為非水溶性之樹脂。 In addition, the upper limit of the softening temperature of the resin having oxygen permeability is preferably 290°C or lower, more preferably 280°C or lower, and even more preferably 270°C or lower. In addition, the material (resin) of the (A) oxygen-permeable membrane 14 used in this embodiment is preferably insoluble in the electrolyte. For example, when the electrolyte is an aqueous system, it is preferably a water-insoluble resin.

形成本實施形態之透氧膜的樹脂，可無限制地使用公知之熱可塑性的透氧性樹脂。上述透氧性樹脂之較佳之23℃透氧度為1.0＊10-15mol/m/(m2．s．Pa)以上。 As the resin forming the oxygen-permeable film of this embodiment, a known thermoplastic oxygen-permeable resin can be used without limitation. The above-mentioned oxygen-permeable resin preferably has an oxygen permeability at 23° C. of 1.0 * 10 -15 mol/m/(m 2 .s.Pa) or more.

作為上述透氧性樹脂之具體例，可舉例如聚4-甲基-1-戊烯、聚丁烯等之聚烯烴；聚四氟乙烯等之氟化碳樹脂；聚二甲基矽氧烷等之聚矽氧。於此，例如屬於聚4-甲基-1-戊烯之市售物的三井化學公司製TPX(註冊商標)(品牌名MX002)之透氧度，根據該公司之製品型錄為9.40＊10-15mol/m/(m2．s．Pa)。 Specific examples of the oxygen-permeable resin include polyolefins such as poly-4-methyl-1-pentene and polybutene; fluorinated carbon resins such as polytetrafluoroethylene; and polydimethylsiloxane Wait for the silicone. Here, for example, the oxygen permeability of TPX (registered trademark) (brand name MX002) manufactured by Mitsui Chemicals, which is a commercial product of poly 4-methyl-1-pentene, is 9.40 according to the product catalog of the company * 10 -15 mol/m/(m 2 .s.Pa).

(A)透氧膜14之材料較佳為含有選自由聚4-甲基-1-戊烯、聚丁 烯、聚四氟乙烯、聚二甲基矽氧烷所構成群之任一種樹脂，更佳為含有聚4-甲基-1-戊烯。 (A) The material of the oxygen-permeable membrane 14 preferably contains any resin selected from the group consisting of poly4-methyl-1-pentene, polybutene, polytetrafluoroethylene, and polydimethylsiloxane, More preferably, it contains poly 4-methyl-1-pentene.

(A)透氧膜14之膜厚係由抑制電解液12滲漏的觀點而言，較佳為0.1μm以上、更佳為1μm以上、再更佳為10μm以上。 (A) The film thickness of the oxygen-permeable membrane 14 is preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 10 μm or more from the viewpoint of suppressing leakage of the electrolytic solution 12.

又，由提升透氧性的觀點而言，(A)透氧膜14之膜厚最好較薄。本實施形態之(A)透氧膜14之厚度較佳為280μm以下。(A)透氧膜14之厚度更佳為250μm以下、再更佳為200μm以下、又更佳為100μm以下、特佳為50μm以下。(A)透氧膜14之厚度特佳為40μm以下。 In addition, from the viewpoint of improving oxygen permeability, the thickness of the (A) oxygen-permeable film 14 is preferably thin. The thickness of the (A) oxygen-permeable membrane 14 of this embodiment is preferably 280 μm or less. (A) The thickness of the oxygen-permeable membrane 14 is more preferably 250 μm or less, still more preferably 200 μm or less, still more preferably 100 μm or less, and particularly preferably 50 μm or less. (A) The thickness of the oxygen-permeable membrane 14 is particularly preferably 40 μm or less.

如上述，對於(A)透氧膜14係要求最好不通過電解液12的特性。而此係與薄膜化之間具有權衡關係之性能。 As described above, the characteristics of (A) the oxygen-permeable membrane 14 system preferably do not pass through the electrolyte 12. And this is a performance that has a trade-off relationship with thinning.

習知，使用一般所使用之技術之塗佈法而得的膜，於形成清漆之溶媒之乾燥時，由於有併發收縮之可能性等，而有發生針孔等的情形。因此，膜厚必須某程度加厚。又，視(B)導電性基材15之微觀層次之形狀，而產生降低清漆濃度，以使其容易滲透至(B)導電性基材15之表面的必要。此時，亦有因溶媒蒸發而針孔發生機率增高的情形。 It is known that when using a coating method using a commonly used technique, when the solvent forming the varnish is dried, pinholes and the like may occur due to the possibility of concurrent shrinkage and the like. Therefore, the film thickness must be increased to some extent. In addition, depending on the shape of the (B) conductive substrate 15 at the micro level, there is a need to reduce the concentration of the varnish so that it can easily penetrate into the surface of the (B) conductive substrate 15. At this time, there is also a case where the probability of pinhole occurrence increases due to solvent evaporation.

相對於此，本實施形態之(A)透氧膜14，具體而言為熱可塑性樹脂膜，故可事先作成較薄之薄膜。藉由使其與(B)導電性基材15壓黏、或融黏，可獲得薄且不發生電解液12滲漏的積層體(空氣電極)。再者，壓黏等之手法亦被認為適合用於形成使(AB)透氧膜‧導電性基材混合層145密集地存在於(A)透氧膜14之材料與(B)導電性基材15間的態樣。 In contrast, the (A) oxygen-permeable membrane 14 of the present embodiment is specifically a thermoplastic resin film, so a thin film can be made in advance. By press-bonding or fusing with the (B) conductive substrate 15, a thin laminate (air electrode) without leakage of the electrolyte 12 can be obtained. In addition, techniques such as pressure bonding are also considered to be suitable for forming (AB) oxygen-permeable film ‧ conductive substrate mixed layer 145 densely present in the materials of (A) oxygen-permeable film 14 and (B) conductive group 15 appearances.

根據此等理由，以熱可塑性樹脂膜作為(A)透氧膜14之態樣， 有利於作為本實施形態之燃料電池之空氣電極13的材料。 For these reasons, using the thermoplastic resin film as the (A) oxygen-permeable membrane 14 is advantageous as the material of the air electrode 13 of the fuel cell of this embodiment.

此種(A)透氧膜14，視需要依賦予強度等目的，亦可併用外框等支撐材等。 Such an (A) oxygen-permeable membrane 14 may be used in combination with a supporting material such as an outer frame according to the purpose of giving strength and the like as necessary.

另一方面，在需要強度等的態樣中，亦有需要(A)透氧膜14為較厚態樣的情形。藉由習知之塗佈手法獲得某程度以上之厚度的膜時，將有難以去除用於調製清漆所必要之溶媒的情形。視溶媒種類，亦有對電解液性能造成不良影響之虞。因此，有必須進行複數次塗佈步驟、予以加厚之步驟的情形。此方法認為將有耗費工程與時間、品質管理變得困難的可能性。 On the other hand, in the aspect requiring strength and the like, there may be a case where (A) the oxygen-permeable membrane 14 is a thick aspect. When a film of a certain thickness or more is obtained by a conventional coating method, it may be difficult to remove the solvent necessary for preparing the varnish. Depending on the type of solvent, there is also the risk of adversely affecting the performance of the electrolyte. Therefore, it is necessary to perform a plurality of coating steps and thickening steps. This method believes that there is a possibility that it will be difficult to consume engineering and time, and quality management.

以本實施形態之熱可塑性樹脂膜作為(A)透氧膜14的態樣中，已知在使用壓黏之方法時，亦容易製造具有較厚之(A)透氧膜14之空氣電極。 With the thermoplastic resin film of this embodiment as the aspect of the (A) oxygen-permeable membrane 14, it is known that when the pressure bonding method is used, it is also easy to manufacture the air electrode having the thicker (A) oxygen-permeable membrane 14.

作為此種情況之(A)透氧膜14的厚度，為例如1000μm以下、較佳為500μm以下、更佳為200μm以下、再更佳為100μm以下、又更佳為50μm以下。 The thickness of the (A) oxygen-permeable membrane 14 in this case is, for example, 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and still more preferably 50 μm or less.

另一方面，厚度之較佳下限值係如上述般，較佳為0.1μm以上、更佳為1μm以上。 On the other hand, the preferable lower limit of the thickness is as described above, preferably 0.1 μm or more, and more preferably 1 μm or more.

作為(B)導電性基材15之材料，燃料電極11之導電性基材之材料係可列舉上述者。 As the material of (B) the conductive base material 15, the material of the conductive base material of the fuel electrode 11 may include the above.

(B)導電性基材15可由與燃料電極11之導電性基材相同材料所形成，亦可由不同材料所形成。 (B) The conductive substrate 15 may be formed of the same material as the conductive substrate of the fuel electrode 11 or may be formed of different materials.

(B)導電性基材15較佳係由透氧性及對水之滲透性優越之材料所構成，較佳係由碳布、碳紙、碳氈等碳材料所構成。 (B) The conductive substrate 15 is preferably composed of a material having excellent oxygen permeability and permeability to water, and is preferably composed of carbon materials such as carbon cloth, carbon paper, and carbon felt.

在(B)導電性基材15為片材狀時，由穩定地載持電極 觸媒之觀點而言，(B)導電性基材15之厚度較佳為10μm以上、更佳為100μm以上。又，由空氣電極13之小型化的觀點而言，(B)導電性基材15之厚度較佳為5mm以下、更佳為1mm以下。 When (B) the conductive substrate 15 is in the form of a sheet, from the viewpoint of stably supporting the electrode catalyst, the thickness of the (B) conductive substrate 15 is preferably 10 m or more, and more preferably 100 m or more. In addition, from the viewpoint of miniaturization of the air electrode 13, (B) the thickness of the conductive substrate 15 is preferably 5 mm or less, and more preferably 1 mm or less.

又，空氣電極13中，電極觸媒係載持於例如(B)導電性基材15。電極觸媒較佳係作為(C)電極觸媒層19而設置。 In the air electrode 13, the electrode catalyst is carried on, for example, (B) the conductive substrate 15. The electrode catalyst is preferably provided as (C) electrode catalyst layer 19.

圖2(a)及圖2(b)係表示作為空氣電極13所使用之電極的構成例的剖面圖。如圖2(a)及圖2(b)所示，空氣電極13係具有(C)電極觸媒層19。(C)電極觸媒層19較佳係設於(B)導電性基材15之表面、即與(A)透氧膜14間之接合面之背面，將電極觸媒配置為層狀而成。 2(a) and 2(b) are cross-sectional views showing an example of the configuration of an electrode used as the air electrode 13. As shown in FIGS. 2( a) and 2 (b ), the air electrode 13 has (C) an electrode catalyst layer 19. (C) The electrode catalyst layer 19 is preferably provided on the surface of the (B) conductive substrate 15, that is, the back surface of the bonding surface with the (A) oxygen-permeable membrane 14, and the electrode catalyst is arranged in a layer .

(C)電極觸媒層19可形成於(B)導電性基材15之上述背面之全體，亦可形成於一部分。較佳係形成於上述背面之全體。又，(C)電極觸媒層19可為由片材狀、薄膜狀之觸媒所形成的層，亦可為由粒子狀之觸媒所形成的層。粒子狀之觸媒即使彼此不相接只要整體形成為層即可。又，於層形成時，可採用例如併用黏結劑樹脂等公知之技術。 (C) The electrode catalyst layer 19 may be formed on the entire back surface of the conductive substrate 15 (B), or may be formed on a part of it. It is preferably formed on the entire back surface. In addition, (C) the electrode catalyst layer 19 may be a layer formed of a sheet-shaped or thin-film catalyst, or a layer formed of a particulate catalyst. Even if the particulate catalysts are not in contact with each other, they may be formed as a layer as a whole. In addition, when forming the layer, a well-known technique such as a binder resin may be used in combination.

由擴寬於空氣電極13之比表面積、提高反應效率的觀點而言，(C)電極觸媒層19之厚度最好較薄。較佳為1nm以上、更佳為10nm以上。另一方面，較佳上限值為1000nm以下、更佳為500nm以下、再更佳為100nm以下。又，由同樣的觀點而言，每單位電極表面積之觸媒物質量較佳為0.01~10μmol/cm2、更佳為0.1~5μmol/cm2。 From the viewpoint of widening the specific surface area of the air electrode 13 and improving the reaction efficiency, the thickness of the (C) electrode catalyst layer 19 is preferably thin. It is preferably 1 nm or more, and more preferably 10 nm or more. On the other hand, the preferred upper limit value is 1000 nm or less, more preferably 500 nm or less, and even more preferably 100 nm or less. From the same viewpoint, the mass of the catalyst per unit electrode surface area is preferably 0.01 to 10 μmol/cm 2 , and more preferably 0.1 to 5 μmol/cm 2 .

作為(C)電極觸媒層19所使用之電極觸媒的具體例，可舉例如金屬觸媒。又，作為電極觸媒之材料，由藉由空氣電極13進行觸媒反應的觀點而言，例如含有選自由Ru、Rh、Ir、Ni、Pd、 Pt、Cu、Ag及Au所構成群之1種或2種以上金屬，較佳為含有Ru、Rh、Pd、Pt或Ag，更佳為含有Pt。此時，由依較少觸媒量獲得高輸出的觀點而言，更佳係於(B)導電性基材15之表面設置含Pt之(C)電極觸媒層19。又，(C)電極觸媒層19較佳為薄膜狀，更佳係設有含Pt之電極觸媒之濺鍍層。 As a specific example of the electrode catalyst used in (C) electrode catalyst layer 19, a metal catalyst can be mentioned, for example. In addition, as the material of the electrode catalyst, from the viewpoint of performing the catalyst reaction by the air electrode 13, for example, it contains one selected from the group consisting of Ru, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au One or two or more metals preferably contain Ru, Rh, Pd, Pt or Ag, and more preferably contain Pt. At this time, from the viewpoint of obtaining high output with a smaller amount of catalyst, it is more preferable to provide the (C) electrode catalyst layer 19 containing Pt on the surface of the (B) conductive substrate 15. In addition, (C) the electrode catalyst layer 19 is preferably in the form of a thin film, and it is more preferably provided with a sputtering layer containing an electrode catalyst containing Pt.

在空氣電極13全體之形狀為片材狀時，空氣電極13之厚度係由維持強度的觀點而言，較佳為20μm以上、更佳為100μm以上。又，由空氣電極13之小型化的觀點而言，空氣電極13之厚度較佳為7mm以下、更佳為5mm以下、再更佳為2mm以下、又更佳為1mm以下。 When the overall shape of the air electrode 13 is a sheet, the thickness of the air electrode 13 is preferably 20 μm or more, and more preferably 100 μm or more from the viewpoint of maintaining strength. From the viewpoint of miniaturization of the air electrode 13, the thickness of the air electrode 13 is preferably 7 mm or less, more preferably 5 mm or less, still more preferably 2 mm or less, and still more preferably 1 mm or less.

接著，說明使用作為空氣電極13之燃料電池用電極的製造方法。 Next, a manufacturing method using the fuel cell electrode as the air electrode 13 will be described.

本實施形態中，使用作為空氣電極13之電極，例如包含： In this embodiment, the electrode used as the air electrode 13 includes, for example:

(步驟1)藉由(B)導電性基材15與(A)透氧膜14依直接相接之狀態進行壓黏，而將(B)導電性基材15與(A)透氧膜14接黏的步驟；以及 (Step 1) By (B) the conductive substrate 15 and the (A) oxygen-permeable membrane 14 being pressure-bonded in a state of being directly in contact, the (B) conductive substrate 15 and (A) the oxygen-permeable membrane 14 Bonding steps; and

(步驟2)於(B)導電性基材15將電極觸媒固定化的步驟。 (Step 2) The step of fixing the electrode catalyst on the conductive substrate 15 in (B).

步驟1及步驟2之順序並無限制，但由將電極觸媒穩定地固定化於(B)導電性基材15的觀點而言，較佳係在進行步驟1後，再進行步驟2。 The order of Step 1 and Step 2 is not limited, but from the viewpoint of stably fixing the electrode catalyst to the (B) conductive substrate 15, it is preferable to perform Step 2 after performing Step 1.

作為壓黏之方法，可無限制地使用壓製成型、(共)擠出成形、沖壓模具成形、加壓成形、真空成型等可實現壓黏狀態的公知成形方法。其中，由樹脂之適用範圍寬度而言，以壓製成型(熔融壓製成型或固相壓製成型)為適合例，由生產性高度的觀點而言，以(共) 擠出成形為適合例。以下，以壓製成型為例進行說明。 As the method of pressure bonding, known forming methods that can achieve a pressure bonding state, such as press molding, (co)extrusion molding, stamping die molding, press molding, and vacuum molding, can be used without limitation. Among them, in terms of the application range of the resin, compression molding (melt compression molding or solid-phase compression molding) is a suitable example, and from the viewpoint of high productivity, (co)extrusion molding is a suitable example. Hereinafter, press molding will be described as an example.

圖3(a)及圖3(b)係說明步驟1之例的剖面圖。 3(a) and 3(b) are cross-sectional views illustrating an example of step 1.

具體而言，如圖3(a)所示，首先，於對向配置之加熱板21a及加熱板21b之間直接重疊配置(A)透氧膜14及(B)導電性基材15。然後，將重疊之(A)透氧膜14及(B)導電性基材15藉由加熱板21a及加熱板21b夾持，利用熱壓黏進行一體化，藉此獲得(A)透氧膜14及(B)導電性基材15之積層體。另外，亦可使用一邊由擠出成形機排出(A)透氧膜14、一邊壓黏至(B)導電性基材15的擠出層合加工。 Specifically, as shown in FIG. 3( a ), first, the (A) oxygen-permeable film 14 and (B) the conductive base material 15 are directly overlapped between the opposed heating plate 21 a and the heating plate 21 b. Then, the (A) oxygen permeable membrane 14 and (B) conductive substrate 15 are sandwiched by the heating plate 21a and the heating plate 21b, and integrated by hot-press bonding to obtain the (A) oxygen permeable membrane 14 and (B) The laminate of the conductive substrate 15. In addition, an extrusion lamination process in which (A) the oxygen-permeable membrane 14 is discharged from the extrusion molding machine while being pressure-bonded to the (B) conductive substrate 15 may also be used.

熱壓黏之條件並無限制。壓黏時之溫度較佳係較(A)透氧膜14之原料樹脂之融點低10~80℃之範圍的溫度，更佳係低10~60℃之範圍的溫度。尤其在使作為(A)透氧膜14之原料樹脂之聚4-甲基-1-戊烯熱壓黏的情況，較佳係140~210℃之溫度、更佳係160~210℃之溫度、再更佳係170℃~200℃之溫度。壓黏時之壓力較佳係0.1~10MPa之壓力、更佳係0.5~5MPa之壓力、再更佳係0.5~2MPa之壓力。 The conditions for hot pressing are not limited. The temperature during pressure bonding is preferably a temperature lower than the melting point of the raw material resin of (A) the oxygen-permeable membrane 14 by a range of 10 to 80°C, and more preferably a temperature lower by a range of 10 to 60°C. Especially in the case of thermocompression bonding poly4-methyl-1-pentene which is the raw material resin of (A) oxygen permeable membrane 14, the temperature is preferably 140 to 210°C, more preferably 160 to 210°C , Even better is the temperature of 170 ℃ ~ 200 ℃. The pressure during pressing is preferably 0.1 to 10 MPa, more preferably 0.5 to 5 MPa, and even more preferably 0.5 to 2 MPa.

另一方面，亦有使樹脂依融點或玻璃轉移溫度以上之溫度熔融而與導電性基材接觸後，進行冷卻壓製的方法。此時，可舉例如使樹脂熔融之溫度係依較上述融點或玻璃轉移溫度高10~50℃之溫度使樹脂熔融、流動，依與導電性基材接觸之狀態進行壓製，並依室溫~較上述融點或玻璃轉移溫度低10℃以上之溫度進行冷卻的方法。此時之壓力可設為較上述壓力低。 On the other hand, there is also a method in which the resin is melted at a temperature higher than the melting point or glass transition temperature and brought into contact with the conductive base material, and then cooled and pressed. In this case, for example, the temperature at which the resin is melted is melted and flowed at a temperature higher than the melting point or the glass transition temperature by 10 to 50° C., pressed in contact with the conductive substrate, and at room temperature. ~ A method of cooling at a temperature 10°C or more lower than the above melting point or glass transition temperature. The pressure at this time can be set lower than the above pressure.

又，在使(B)導電性基材15與(A)透氧膜14藉由(共)擠出成形進行積層時，於擠出階段之樹脂溫度係上述融點或玻璃轉移溫度以 上；使(B)導電性基材15與(A)透氧膜14接觸之階段的樹脂溫度，較佳係較上述融點或玻璃轉移溫度低10~80℃之範圍的溫度，更佳係低10~60℃之範圍的溫度。此外，較佳係使用雙輥等使上述(B)導電性基材15與(A)透氧膜14壓黏的方法。 In addition, when (B) the conductive substrate 15 and (A) the oxygen-permeable membrane 14 are laminated by (co)extrusion molding, the resin temperature at the extrusion stage is above the melting point or glass transition temperature; (B) The temperature of the resin when the conductive substrate 15 is in contact with the (A) oxygen-permeable membrane 14 is preferably a temperature in the range of 10 to 80°C lower than the melting point or glass transition temperature, and more preferably 10 to A temperature in the range of 60°C. In addition, it is preferable to press-bond the above-mentioned (B) conductive base material 15 and (A) oxygen-permeable film 14 using a double roller or the like.

又，步驟2係包含例如於(B)導電性基材15之表面，藉由濺鍍法或電極還原法等，形成含Pt之(C)電極觸媒層19的步驟，較佳係藉由濺鍍法形成含Pt之(C)電極觸媒層19的步驟。 Furthermore, step 2 includes, for example, the step of forming the (C) electrode catalyst layer 19 containing Pt on the surface of the (B) conductive substrate 15 by sputtering or electrode reduction method, preferably by The step of forming the (C) electrode catalyst layer 19 containing Pt by the sputtering method.

濺鍍之條件並無限制，關於溫度、時間等條件，只要在可進行濺鍍且不發生材料(基材)劣化的範圍內實施即可。 The conditions of sputtering are not limited, and conditions such as temperature and time may be implemented within a range where sputtering can be performed without deterioration of the material (substrate).

又，作為步驟2之其他方法，可舉例如調製含有使電極觸媒載持於碳粒子而得之觸媒載持粒子與高分子電解質的塗佈液，將其塗佈於(B)導電性基材15並乾燥，藉此將電極觸媒固定化於(B)導電性基材15的方法。 In addition, as another method of step 2, for example, a coating solution containing catalyst-supporting particles obtained by supporting electrode catalysts on carbon particles and a polymer electrolyte may be prepared and applied to (B) conductivity The base material 15 is dried to thereby fix the electrode catalyst to (B) the conductive base material 15.

根據以上所述，可得到使用作為空氣電極13之電極。 According to the above, an electrode used as the air electrode 13 can be obtained.

然後，例如將載持了微生物(發電菌等)之燃料電極11及空氣電極13配置於容器18之既定位置並經由外部電阻17予以連接，對容器18內供給電解液12，藉此可得到燃料電池10。 Then, for example, the fuel electrode 11 and the air electrode 13 carrying microorganisms (power generating bacteria, etc.) are arranged at predetermined positions of the container 18 and connected via an external resistor 17, and the electrolyte 12 is supplied into the container 18, thereby obtaining fuel Battery 10.

(燃料電池) (The fuel cell)

本實施形態所得之燃料電池10中，空氣電極13係具有包含(A)透氧膜14及(B)導電性基材15、以及位於其之間的滿足特定要件之(AB)透氧膜‧導電性基材混合層145的構造。又，燃料電池10之空氣電極13較佳係(A)透氧膜14與(B)導電性基材15直接相接並壓黏的形態。因此，可依簡便構造獲得高輸出。 In the fuel cell 10 obtained in this embodiment, the air electrode 13 includes an (A) oxygen-permeable membrane 14 and (B) conductive substrate 15 and an (AB) oxygen-permeable membrane located therebetween that satisfies specific requirements The structure of the conductive base material mixed layer 145. In addition, the air electrode 13 of the fuel cell 10 is preferably in a form where (A) the oxygen-permeable membrane 14 and (B) the conductive substrate 15 are directly in contact and pressure-bonded. Therefore, high output can be obtained with a simple structure.

本實施形態之燃料電池10係如上述，由於具有特定之電極構 造，故可例如於-50℃以上、包含室溫之300℃以下的溫度環境下使用。本實施形態之燃料電池10可適合使用作為於此種溫度區域下作動之用途的電源。例如，一般之固定型電源之外，亦有可使用作為車輛等行動領域電源的可能性。 As described above, the fuel cell 10 of this embodiment has a specific electrode structure, and therefore can be used in a temperature environment of -50°C or higher and 300°C or lower including room temperature, for example. The fuel cell 10 of the present embodiment can be suitably used as a power source for operation in such a temperature range. For example, in addition to general fixed power supplies, there is a possibility that they can be used as power supplies for vehicles and other mobile fields.

以下例示本實施形態之燃料電池之適合活用態樣。 The following is an example of suitable use of the fuel cell of this embodiment.

本實施形態之燃料電池若具有含氫之燃料物質即可進行發電，故不需要大規模之發電設備或送電線等之建設等。因此，認為適合作為大多設於郊外或荒野等之(大規模)農場或(大規模)牧場之(輔助)電源。其中，在採用MFC之形態時可例示如以下般之活用法。 The fuel cell of this embodiment can generate electricity if it contains a hydrogen-containing fuel substance, so there is no need for the construction of large-scale power generation equipment or transmission lines. Therefore, it is considered suitable as an (auxiliary) power supply for (large-scale) farms or (large-scale) pastures, which are mostly installed in the countryside or wilderness. Among them, the following usages can be exemplified when adopting the form of MFC.

於牧場中，可適合於電燈或擠乳機、飼料之配送系統之動力源、其他生活用電源等，且可不論日夜適時地利用。作為MFC之燃料，由於可活用家畜***物，故亦可由家畜獲得燃料之一部分或全部。 In the pasture, it can be suitable for power sources of electric lights or milking machines, feed distribution systems, other power sources for daily use, etc., and can be used at any time regardless of day and night. As the fuel of MFC, since the excreta of livestock can be utilized, some or all of the fuel can also be obtained from livestock.

於農場中，可舉例如活用作為水或培養液之送液、循環系統之動力源、或收穫裝置或電燈等之(輔助)電源。又，亦可在使植物收穫後等所產生之非可食用部(葉或莖等)例如堆肥化後，將其一部分或全部作為燃料電池之燃料。又，在農場與牧場共同營運的情況，亦可將上述植物之非可食用部供給給家畜，並將其***物活用作為燃料電池之燃料。如此，認為有可構築成整體之能量效率高之畜產系統、植物栽培系統、其等之複合系統的可能性。 On the farm, for example, it is possible to utilize (auxiliary) power supply as water or culture solution feed, power source of circulation system, harvesting device or electric lamp. In addition, after composting the non-edible parts (leaves, stems, etc.) generated after the plants are harvested, a part or all of them may be used as fuel for the fuel cell. In addition, when the farm and ranch are jointly operated, the non-edible parts of the above plants can be supplied to livestock, and their waste can be used as fuel for the fuel cell. In this way, it is considered that there is a possibility of constructing an overall energy efficient animal production system, a plant cultivation system, and other composite systems.

以上陳述了本發明之實施形態，但此等為本發明之例示，亦可採用上述以外之各種構成。 The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above may be adopted.

[實施例] [Example]

以下藉由實施例更具體地說明本發明，但本發明在不 逾越其主旨之前提下，不受限於以下之實施例。 Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to the following examples without exceeding the gist.

首先，以下表示空氣電極及燃料電極之製作例。 First, the following shows an example of manufacturing an air electrode and a fuel electrode.

(空氣電極製作例1) (Production example 1 of air electrode)

使用碳布(AvCarb公司製，HCB1071，厚350μm)作為導電性基材、使用聚4-甲基-1-戊烯(三井化學公司製TPX，MX0020)之薄膜(厚27μm)作為透氧膜，分別將各1片重疊並藉由熱壓製(180℃、3MPa)進行壓黏，得到聚4-甲基-1-戊烯/碳布壓黏薄膜。 A carbon cloth (manufactured by AvCarb Corporation, HCB1071, thickness 350 μm) was used as a conductive substrate, and a film (thickness 27 μm) of poly 4-methyl-1-pentene (TPX, MX0020 manufactured by Mitsui Chemicals Co., Ltd.) was used as an oxygen-permeable membrane. Each one piece was overlapped and pressed by hot pressing (180° C., 3 MPa) to obtain a poly 4-methyl-1-pentene/carbon cloth pressed film.

將所得壓黏薄膜切取為縱130mm×橫60mm，將於5wt%之Nafion Perfluorinated resin(納菲全氟樹脂)溶液(SIGMA Aldrich公司製)1.2mL中加入了蒸餾水1.8mL與Pt/C(Pt 37.5wt%，田中貴金屬公司製TEC10E40E)105mg的懸浮液塗佈於碳布側之表面，依2.56μmol/cm2使其附著。於室溫下乾燥12小時後，連接導線而製作空氣電極a。 The obtained pressure-sensitive adhesive film was cut into a length of 130 mm × a width of 60 mm, and 1.8 mL of distilled water and Pt/C (Pt 37.5) were added to 1.2 mL of a 5 wt% Nafion Perfluorinated resin solution (manufactured by SIGMA Aldrich). wt%, TEC10E40E manufactured by Tanaka Precious Metal Co., Ltd.) 105 mg of the suspension was coated on the surface of the carbon cloth side, and adhered according to 2.56 μmol/cm 2 . After drying at room temperature for 12 hours, the wires were connected to produce an air electrode a.

藉碳膜補強空氣電極a之表面後，對經切削加工之剖面藉由日立製作所公司製S-4800型掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)。 After the surface of the air electrode a was reinforced with a carbon film, the cut cross-section was observed with a S-4800 scanning electron microscope manufactured by Hitachi, Ltd., and it was confirmed that a densely mixed layer of conductive substrate and TPX resin (TPX The gap occupancy rate: 100%).

(空氣電極製作例2) (Air electrode manufacturing example 2)

使用空氣電極製作例1所得之縱130mm×橫60mm的碳布/聚4-甲基-1-戊烯壓黏薄膜，於碳布側之表面藉由濺鍍使Pt依0.26μmol/cm2附著成層狀。其後，連接導線而製作空氣電極b。 The carbon cloth/poly 4-methyl-1-pentene pressure-bonded film with a length of 130 mm and a width of 60 mm obtained by the air electrode manufacturing example 1 was used to adhere Pt to 0.26 μmol/cm 2 on the surface of the carbon cloth by sputtering Layered. Thereafter, the lead wire was connected to produce an air electrode b.

依與空氣電極製作例1相同之方法對空氣電極b藉由掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)。 The air electrode b was observed with a scanning electron microscope in the same manner as in Air Electrode Manufacturing Example 1, and a densely mixed layer of a conductive substrate and TPX resin was confirmed (gap occupancy rate of TPX: 100%).

(空氣電極製作例3) (Production Example 3 of Air Electrode)

除了調整濺鍍條件使Pt依0.03μmol/cm2附著以外，其他依照空氣電極製作例2製作空氣電極c。 An air electrode c was prepared according to Air electrode preparation example 2 except that the sputtering conditions were adjusted so that Pt adhered at 0.03 μmol/cm 2 .

依與空氣電極製作例1相同之方法對空氣電極c藉由掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)。 The air electrode c was observed with a scanning electron microscope in the same manner as the air electrode manufacturing example 1, and a densely mixed layer of a conductive substrate and TPX resin (gap occupancy rate of TPX: 100%) was confirmed.

(空氣電極製作例4) (Air electrode manufacturing example 4)

除了取代碳布而使用碳紙(AvCarb公司製P50，厚170μm)作為導電性基材以外，其他依照空氣電極製作例1製作空氣電極d。 An air electrode d was produced in accordance with Air Electrode Production Example 1 except that carbon paper (P50 manufactured by AvCarb Corporation, 170 μm thick) was used as the conductive substrate instead of carbon cloth.

依與空氣電極製作例1相同之方法對空氣電極d藉由掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)。 The air electrode d was observed with a scanning electron microscope in the same manner as in Air Electrode Manufacturing Example 1, and a densely mixed layer of a conductive substrate and TPX resin (gap occupancy rate of TPX: 100%) was confirmed.

(空氣電極製作例5) (Example 5 of making air electrode)

除了取代碳布而使用碳紙(AvCarb公司製P50，厚170μm)作為導電性基材以外，其他依照空氣電極製作例2製作空氣電極e。 An air electrode e was produced in accordance with Air Electrode Production Example 2 except that carbon paper (P50 manufactured by AvCarb, 170 μm thick) was used as the conductive substrate instead of carbon cloth.

依與空氣電極製作例1相同之方法對空氣電極e藉由掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)(上述圖4)。 The air electrode e was observed with a scanning electron microscope in the same manner as in Air Electrode Manufacturing Example 1, and a densely mixed layer of conductive substrate and TPX resin was confirmed (gap occupancy rate of TPX: 100%) (above figure 4).

(空氣電極製作例6) (Air electrode manufacturing example 6)

除了使Pt依0.03μmol/cm2附著以外，其他依照空氣電極製作例5製作空氣電極f。 Except for attaching Pt at 0.03 μmol/cm 2 , the air electrode f was prepared according to Air electrode preparation example 5.

依與空氣電極製作例1相同之方法對空氣電極f藉由掃描型電子顯微鏡進行觀察，確認到導電性基材與TPX樹脂之密集混合的層(TPX之間隙佔有率：100%)。 The air electrode f was observed with a scanning electron microscope in the same manner as the air electrode manufacturing example 1, and a densely mixed layer of a conductive base material and TPX resin (gap occupancy rate of TPX: 100%) was confirmed.

(空氣電極製作例7) (Example 7 of making air electrode)

使用碳布(AvCarb公司製，HCB1071，厚350μm)作為導電性基材，以於聚四氟乙烯(PTFE)之60%水懸浮液(SIGMA Aldrich公司製)添加了碳黑(Valcan XC-72，Cabot公司製)之懸浮液作為清漆塗佈於單面，而製作塗佈了聚四氟乙烯作為透氧膜的碳布/聚四氟乙烯塗佈薄膜。 Carbon cloth (manufactured by AvCarb Corporation, HCB1071, thickness 350 μm) was used as a conductive substrate, and carbon black (Valcan XC-72, Valcan XC-72, The suspension of Cabot Co., Ltd. was applied as a varnish on one side, and a carbon cloth/polytetrafluoroethylene coated film coated with polytetrafluoroethylene as an oxygen-permeable membrane was prepared.

將所得塗佈薄膜切取為縱130mm×橫60mm，依照空氣電極製作例1於碳布側之表面塗佈Pt/C，使Pt依2.56μmol/cm2附著。於室溫下乾燥12小時後，連接導線而製作空氣電極j。透氧膜之厚度為300μm。 The obtained coating film was cut out to be 130 mm long×60 mm wide, and Pt/C was coated on the surface of the carbon cloth side according to Air Electrode Preparation Example 1, so that Pt was adhered at 2.56 μmol/cm 2 . After drying at room temperature for 12 hours, the wires were connected to produce an air electrode j. The thickness of the oxygen-permeable membrane is 300 μm.

(空氣電極製作例8) (Example 8 of making air electrode)

除了依Pt成為0.26μmol/cm2之方式使Pt/C附著以外，其他依照空氣電極製作例7製作空氣電極k。透氧膜之厚度為300μm。 Except for attaching Pt/C so that Pt became 0.26 μmol/cm 2, the air electrode k was prepared according to Air electrode preparation example 7. The thickness of the oxygen-permeable membrane is 300 μm.

(空氣電極製作例9) (Example 9 of making air electrode)

除了取代碳布而使用碳紙(AvCarb公司製P50，厚170μm)作為導電性基材以外，其他依照空氣電極製作例7製作空氣電極1。透氧膜之厚度為300μm。 The air electrode 1 was produced according to the air electrode production example 7 except that carbon paper (P50 manufactured by AvCarb Co., Ltd., thickness 170 μm) was used instead of the carbon cloth as the conductive substrate. The thickness of the oxygen-permeable membrane is 300 μm.

(空氣電極製作例10) (Air electrode manufacturing example 10)

將作為導電性基材之碳布(AvCarb公司製，HCB1071，厚350μm)切取為縱130mm×橫60mm，僅於單面藉由濺鍍使Pt依0.26μmol/cm2附著為層狀後，連接導線。對碳布之未附著Pt側之面，將作為透氧膜之縱130mm×橫60mm×厚27μm之聚4-甲基-1-戊烯之薄膜整面塗佈環氧接黏劑並接黏，製作空氣電極m。 A carbon cloth (made by AvCarb Corporation, HCB1071, 350 μm thick) was cut into a length of 130 mm × 60 mm in width, and Pt was attached to the layer by 0.26 μmol/cm 2 by sputtering only on one side, and then connected wire. On the surface of the carbon cloth that is not attached to the Pt side, apply an epoxy adhesive to the entire surface of the polyoxymethyl 4-pentan-1-pentene film, which is 130 mm in length × 60 mm in width × 27 μm thick as an oxygen-permeable film, and adhere , Making an air electrode m.

(燃料電極製作例1) (Fuel electrode manufacturing example 1)

使用碳氈(綜合碳公司製)作為導電性基材，將其切取為縱 130mm×橫60mm，作為燃料電極a。 Carbon felt (manufactured by Comprehensive Carbon Co., Ltd.) was used as a conductive base material, and it was cut out to have a length of 130 mm × a width of 60 mm as a fuel electrode a.

(實施例1~6、比較例1~4) (Examples 1 to 6, Comparative Examples 1 to 4)

使用以上製作之空氣電極及燃料電極製作圖1所示構成的燃料電池10，測定輸出。將各例所使用之電極構成及輸出測定結果示於表1。又，任一燃料電池中，均未發現由空氣電極之電解液滲漏。 Using the air electrode and the fuel electrode prepared above, a fuel cell 10 having the configuration shown in FIG. 1 was produced, and the output was measured. Table 1 shows the electrode configuration and output measurement results used in each example. Furthermore, in any fuel cell, no leakage of electrolyte from the air electrode was found.

(實施例1) (Example 1)

使牛糞懸浮於蒸餾水，依懸浮液中之固形份成為20g/L之方式調製電解液，使用1.0L作為發電用之電解液。 The cow dung was suspended in distilled water, the electrolyte was prepared so that the solid content in the suspension became 20 g/L, and 1.0 L was used as the electrolyte for power generation.

將空氣電極a設置成使附著了Pt之碳布側之面接觸至電解液、透氧膜側之面接觸至空氣，將燃料電極a設置成浸漬於電解液中，製作圖1所示構成的燃料電池。將空氣電極a與燃料電極a經由150Ω之外部電阻進行連接而開始發電試驗，隨著發電而使電解液中所含發電菌附著於燃料電極a。記錄發電菌附著後之輸出最高值為0.39mW。 The air electrode a was set so that the surface on the carbon cloth side with Pt attached was in contact with the electrolyte, and the surface on the oxygen permeable membrane side was in contact with air. The fuel cell. The air electrode a and the fuel electrode a were connected via an external resistance of 150 Ω to start a power generation test, and the power generating bacteria contained in the electrolyte were attached to the fuel electrode a as power was generated. The highest output value after recording the power generating bacteria is 0.39mW.

(實施例2) (Example 2)

除了取代空氣電極a而使用空氣電極b以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.48mW。 Except for using the air electrode b instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.48 mW.

(實施例3) (Example 3)

除了取代空氣電極a而使用空氣電極c以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.39mW。 Except for using the air electrode c instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.39 mW.

(實施例4) (Example 4)

除了取代空氣電極a而使用空氣電極d以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.83mW。 Except for using the air electrode d instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.83 mW.

(實施例5) (Example 5)

除了取代空氣電極a而使用空氣電極e以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.80mW。 Except for using the air electrode e instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.80 mW.

(實施例6) (Example 6)

除了取代空氣電極a而使用空氣電極f以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.60mW。 Except for using the air electrode f instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.60 mW.

(比較例1) (Comparative example 1)

除了取代空氣電極a而使用空氣電極j以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.30mW。 Except for using the air electrode j instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.30 mW.

(比較例2) (Comparative example 2)

除了取代空氣電極a而使用空氣電極k以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.27mW。 Except for using the air electrode k instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.27 mW.

(比較例3) (Comparative example 3)

除了取代空氣電極a而使用空氣電極1以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.30mW。 Except for using the air electrode 1 instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.30 mW.

(比較例4) (Comparative example 4)

除了取代空氣電極a而使用空氣電極m以外，其餘依照實施例1實施發電試驗，記錄輸出最高值為0.05mW。 Except for using the air electrode m instead of the air electrode a, the power generation test was carried out in accordance with Example 1, and the highest recorded output value was 0.05 mW.

[表1]

Figure 108127820-A0101-12-0025-8
[Table 1]
Figure 108127820-A0101-12-0025-8

由上述結果，若使用含有本實施例之特定構成之空氣電極的燃料電池，則可獲得相對較高輸出之電力。可認為此係由於透氧膜相對較薄、且與導電性基材形成適當之混合層，故空氣中之氧於空氣電極中有效率地與氫原子進行反應的結果所致。 From the above results, if a fuel cell containing the air electrode of the specific configuration of this embodiment is used, relatively high output power can be obtained. It is believed that this is because the oxygen permeable film is relatively thin and forms an appropriate mixed layer with the conductive substrate, so the oxygen in the air efficiently reacts with hydrogen atoms in the air electrode.

以下附記參考形態之例。 The following is an example of reference form.

1.一種燃料電池用電極，係於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中，使用於上述空氣電極的電極；其包含導電性基材、電極觸媒及透氧膜，且上述導電性基材與上述透氧膜直接相接並壓黏。 1. An electrode for a fuel cell, comprising an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode, the electrode used for the air electrode; which includes a conductive group Materials, electrode catalysts, and oxygen-permeable membranes, and the conductive substrate is directly in contact with the oxygen-permeable membrane and is pressure-bonded.

2.如1.之燃料電池用電極，其中，上述透氧膜之膜厚為0.1μm以上且1000μm以下。 2. The electrode for a fuel cell according to 1., wherein the film thickness of the oxygen permeable membrane is 0.1 μm or more and 1000 μm or less.

3.如1.或2.之燃料電池用電極，其中，上述燃料電極係包含可定著發電菌之導電性基材。 3. The fuel cell electrode according to 1. or 2., wherein the fuel electrode includes a conductive substrate capable of fixing power-generating bacteria.

4.如1.至3.中任一項之燃料電池用電極，其中，上述燃料電極係包含導電性基材、及作為電極觸媒之發電菌。 4. The fuel cell electrode according to any one of 1. to 3., wherein the fuel electrode system includes a conductive base material and a power-generating bacterium as an electrode catalyst.

5.如1.至4.中任一項之燃料電池用電極，其中，上述空氣電極之上述導電性基材之材料為碳材料。 5. The fuel cell electrode according to any one of 1. to 4., wherein the material of the conductive substrate of the air electrode is a carbon material.

6.如1.至5.中任一項之燃料電池用電極，其中，上述燃料電極係包含由碳材料所構成之導電性基材。 6. The fuel cell electrode according to any one of 1. to 5., wherein the fuel electrode includes a conductive base material composed of a carbon material.

7.如1.至6.中任一項之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材料係包含選自由聚4-甲基-1-戊烯、聚丁烯、聚四氟乙烯、聚二甲基矽氧烷所構成群之任一種樹脂。 7. The fuel cell electrode according to any one of 1. to 6., wherein the material of the oxygen permeable membrane of the air electrode is selected from the group consisting of poly 4-methyl-1-pentene, polybutene, poly Any of the resins composed of tetrafluoroethylene and polydimethylsiloxane.

8.如7.之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材 料係包含聚4-甲基-1-戊烯。 8. The fuel cell electrode according to 7., wherein the material of the oxygen permeable membrane of the air electrode contains poly 4-methyl-1-pentene.

9.如1.至8.中任一項之燃料電池用電極，其中，上述燃料電池係以家畜***物作為燃料。 9. The fuel cell electrode according to any one of 1. to 8., wherein the fuel cell uses livestock excrement as fuel.

10.如1.至9.中任一項之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含選自由Ru、Rh、Ir、Ni、Pd、Pt、Cu、Ag及Au所構成群之1種或2種以上金屬。 10. The fuel cell electrode according to any one of 1. to 9., wherein the material of the electrode catalyst of the air electrode includes a material selected from the group consisting of Ru, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and One or more metals composed of Au.

11.如10.之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含Pt。 11. The fuel cell electrode according to 10., wherein the material of the electrode catalyst of the air electrode contains Pt.

12.如11.之燃料電池用電極，其中，上述空氣電極中，於上述導電性基材之表面設有包含Pt之上述電極觸媒之層。 12. The fuel cell electrode according to 11., wherein the air electrode is provided with a layer of the electrode catalyst containing Pt on the surface of the conductive substrate.

13.一種燃料電池，係具備1.至12.中任一項之燃料電池用電極。 13. A fuel cell comprising the fuel cell electrode according to any one of 1. to 12.

14.如13.之燃料電池，其不包含質子傳導膜作為構成要件。 14. The fuel cell of 13. does not contain a proton conductive membrane as a constituent element.

15.一種燃料電池用電極之製造方法，係於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中，用於空氣電極的電極之製造方法；其包含：藉由導電性基材與透氧膜依直接相接之狀態進行壓黏，而將上述導電性基材與上述透氧膜接黏的步驟；與將電極觸媒固定化於上述導電性基材的步驟。 15. A method for manufacturing an electrode for a fuel cell, which is a method for manufacturing an electrode for an air electrode in a fuel cell provided with an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode; It includes: the step of bonding the conductive substrate and the oxygen permeable film by pressure bonding in a state where the conductive substrate and the oxygen permeable film are directly in contact; and fixing the electrode catalyst to the conductive Steps for sex substrates.

16.如15.之燃料電池用電極之製造方法，其中，將電極觸媒固定化於導電性基材之上述步驟，係包含：於上述導電性基材之表面，藉由濺鍍法或電極還原法，形成含有Pt之上述電極觸媒之層的步驟。 16. The method for manufacturing an electrode for a fuel cell according to 15., wherein the step of fixing the electrode catalyst to the conductive substrate includes: on the surface of the conductive substrate, by sputtering or an electrode In the reduction method, a step of forming a layer of the above-mentioned electrode catalyst containing Pt.

17.如16.之燃料電池用電極之製造方法，其中，形成電極觸媒之層的上述步驟，係藉由上述濺鍍法形成含有Pt之上述層的步驟。 17. The method for manufacturing a fuel cell electrode according to 16., wherein the step of forming the electrode catalyst layer is a step of forming the Pt-containing layer by the sputtering method.

本申請案係主張以2018年8月2日申請之日本申請 案特願2018-145690號為基礎的優先權，並將其所有揭示內容引用於此。 This application claims priority based on Japanese Application No. 2018-145690 filed on August 2, 2018, and all disclosures thereof are incorporated herein.

10‧‧‧燃料電池 10‧‧‧ fuel cell

11‧‧‧燃料電極 11‧‧‧ Fuel electrode

12‧‧‧電解液 12‧‧‧Electrolyte

13‧‧‧空氣電極 13‧‧‧Air electrode

14‧‧‧透氧膜 14‧‧‧Oxygen permeable membrane

15‧‧‧導電性基材 15‧‧‧ conductive substrate

16‧‧‧大氣 16‧‧‧Atmosphere

17‧‧‧外部電阻 17‧‧‧External resistance

18‧‧‧容器 18‧‧‧Container

Claims (20)

一種燃料電池用電極，係使用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中的電極； An electrode for a fuel cell, which is an electrode used in a fuel cell provided with an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode; 上述空氣電極係包含導電性基材、電極觸媒及透氧膜，並為： The air electrode system includes a conductive substrate, an electrode catalyst, and an oxygen-permeable membrane, and is: (A)透氧膜層 (A) Oxygen permeable membrane (AB)透氧膜‧導電性基材混合層 (AB) Oxygen permeable membrane and conductive substrate mixed layer (B)導電性基材層 (B) Conductive substrate layer (C)電極觸媒層之順序的積層構造； (C) The sequential build-up structure of the electrode catalyst layer; 上述(A)層為熱可塑性樹脂層，上述(A)層之厚度為0.1 μm以上且280 μm以下。 The (A) layer is a thermoplastic resin layer, and the thickness of the (A) layer is 0.1 μm or more and 280 μm or less. 一種燃料電池用電極，係使用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池中的電極； An electrode for a fuel cell, which is an electrode used in a fuel cell provided with an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode; 其包含導電性基材、電極觸媒及透氧膜， It contains conductive substrate, electrode catalyst and oxygen permeable membrane, 上述導電性基材與上述透氧膜直接相接並壓黏。 The conductive substrate is directly in contact with the oxygen-permeable membrane and is pressure-bonded. 如請求項2之燃料電池用電極，其中，上述透氧膜之膜厚為0.1 μm以上且1000 μm以下。 The fuel cell electrode according to claim 2, wherein the oxygen permeable membrane has a thickness of 0.1 μm or more and 1000 μm or less. 如請求項1或2之燃料電池用電極，其中，上述空氣電極之上述導電性基材之材料為碳材料。 The fuel cell electrode according to claim 1 or 2, wherein the material of the conductive substrate of the air electrode is a carbon material. 如請求項2之燃料電池用電極，其中，上述透氧膜係包含熱可塑性樹脂。 The fuel cell electrode according to claim 2, wherein the oxygen-permeable membrane contains a thermoplastic resin. 如請求項1或5之燃料電池用電極，其中，上述透氧膜係包含 熱可塑性樹脂，該熱可塑性樹脂由示差掃描熱量測定裝置所決定之融點及玻璃轉移溫度之至少一者為100~300℃之範圍。 The fuel cell electrode according to claim 1 or 5, wherein the oxygen-permeable membrane includes a thermoplastic resin, and at least one of the melting point and the glass transition temperature determined by the differential scanning calorimeter is 100~ 300 ℃ range. 如請求項1或5之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材料係包含選自由聚4-甲基-1-戊烯、聚丁烯、聚四氟乙烯、聚二甲基矽氧烷所構成群之任一種樹脂。 The fuel cell electrode according to claim 1 or 5, wherein the material of the oxygen permeable membrane of the air electrode is selected from poly 4-methyl-1-pentene, polybutene, polytetrafluoroethylene, polydi Any of a group of resins composed of methyl silicone. 如請求項1或5之燃料電池用電極，其中，上述空氣電極之上述透氧膜的材料係包含聚4-甲基-1-戊烯。 The fuel cell electrode according to claim 1 or 5, wherein the material of the oxygen permeable membrane of the air electrode includes poly 4-methyl-1-pentene. 如請求項1或2之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含選自由Ru、Rh、Ir、Ni、Pd、Pt、Cu、Ag及Au所構成群之1種或2種以上金屬。 The fuel cell electrode according to claim 1 or 2, wherein the material of the electrode catalyst of the air electrode includes one selected from the group consisting of Ru, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au One or more than two metals. 如請求項9之燃料電池用電極，其中，上述空氣電極之上述電極觸媒的材料係包含Pt。 The fuel cell electrode according to claim 9, wherein the material of the electrode catalyst of the air electrode contains Pt. 如請求項10之燃料電池用電極，其中，上述空氣電極中，於上述導電性基材之表面設有包含Pt之上述電極觸媒之層。 The fuel cell electrode according to claim 10, wherein the air electrode is provided with a layer of the electrode catalyst containing Pt on the surface of the conductive substrate. 如請求項1或2之燃料電池用電極，其中，上述燃料電極係包含可定著發電菌之導電性基材。 The fuel cell electrode according to claim 1 or 2, wherein the fuel electrode includes a conductive substrate capable of fixing power generating bacteria. 如請求項12之燃料電池用電極，其中，上述燃料電極係包含導電性基材、及作為電極觸媒之發電菌。 The electrode for a fuel cell according to claim 12, wherein the fuel electrode includes a conductive substrate and a power-generating bacterium as an electrode catalyst. 如請求項12之燃料電池用電極，其中，上述燃料電極係包含由碳材料所構成之導電性基材。 The fuel cell electrode according to claim 12, wherein the fuel electrode includes a conductive base material composed of a carbon material. 如請求項1或2之燃料電池用電極，其中，上述燃料電池係以家畜***物作為燃料。 The electrode for a fuel cell according to claim 1 or 2, wherein the fuel cell uses livestock waste as fuel. 一種燃料電池，係具備請求項1或2之燃料電池用電極。 A fuel cell is provided with the fuel cell electrode of claim 1 or 2. 如請求項16之燃料電池，其不包含質子傳導膜作為構成要 件。 The fuel cell according to claim 16 does not contain a proton conductive membrane as a constituent element. 一種燃料電池用電極之製造方法，係用於具備空氣電極、燃料電極、及配置於上述空氣電極與上述燃料電極之間之電解液的燃料電池之空氣電極的電極之製造方法；其包含： A method for manufacturing an electrode for a fuel cell is a method for manufacturing an electrode for an air electrode of a fuel cell having an air electrode, a fuel electrode, and an electrolyte disposed between the air electrode and the fuel electrode; it includes: 藉由導電性基材與透氧膜依直接相接之狀態進行壓黏，而將上述導電性基材與上述透氧膜接黏的步驟；與 The step of bonding the conductive substrate to the oxygen permeable film by pressure bonding the conductive substrate and the oxygen permeable film in a state of direct contact; and 將電極觸媒固定化於上述導電性基材的步驟。 The step of fixing the electrode catalyst to the conductive substrate. 如請求項18之燃料電池用電極之製造方法，其中，將電極觸媒固定化於導電性基材之上述步驟，係包含：於上述導電性基材之表面，藉由濺鍍法或電極還原法，形成含有Pt之上述電極觸媒之層的步驟。 The method for manufacturing an electrode for a fuel cell according to claim 18, wherein the step of fixing the electrode catalyst to the conductive substrate includes: on the surface of the conductive substrate, by sputtering or electrode reduction Method to form a layer of the above-mentioned electrode catalyst containing Pt. 如請求項19之燃料電池用電極之製造方法，其中，形成電極觸媒之層的上述步驟，係藉由上述濺鍍法形成含有Pt之上述層的步驟。 The method for manufacturing an electrode for a fuel cell according to claim 19, wherein the step of forming the electrode catalyst layer is a step of forming the Pt-containing layer by the sputtering method.
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