JP2007287530A - Fuel cell, catalyst suitable for it, and its manufacturing method - Google Patents

Fuel cell, catalyst suitable for it, and its manufacturing method Download PDF

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JP2007287530A
JP2007287530A JP2006114977A JP2006114977A JP2007287530A JP 2007287530 A JP2007287530 A JP 2007287530A JP 2006114977 A JP2006114977 A JP 2006114977A JP 2006114977 A JP2006114977 A JP 2006114977A JP 2007287530 A JP2007287530 A JP 2007287530A
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fuel cell
carbide
yeast
electrode
fuel
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JP4915840B2 (en
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Junichi Ozaki
純一 尾崎
Jun Yamazaki
潤 山崎
Asao Otani
朝男 大谷
Hiroyuki Okamoto
裕行 岡本
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Asahi Breweries Ltd
Gunma University NUC
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Gunma University NUC
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive catalyst for a fuel cell capable of providing high power generation efficiency; and to provide its manufacturing method. <P>SOLUTION: A solid body is formed by molding at least a part of yeast at high pressure, a carbide is obtained by carbonizing the solid body by dry distillation, platinum fine particles are supported to the carbide, and thus this catalyst for a fuel cell is manufactured. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、燃料電池、それに好適な触媒及びその製造方法に関する。   The present invention relates to a fuel cell, a catalyst suitable for the fuel cell, and a method for producing the same.

燃料電池は、固体酸化物形燃料電池、溶融炭酸塩形燃料電池、リン酸形燃料電池、高分子電解質形燃料電池（ＰＥＦＣ）、アルカリ水溶液形燃料電池に分類されうる。燃料電池は、燃料極（マイナス極）と空気極（プラス極）との間に電解質物質を挟んで構成され、この電解質物質の種類によって形式が分類されうる。
特開２００４−３３０１８１号公報 特開２００３−３４２５８４号公報 The fuel cell can be classified into a solid oxide fuel cell, a molten carbonate fuel cell, a phosphoric acid fuel cell, a polymer electrolyte fuel cell (PEFC), and an alkaline aqueous fuel cell. The fuel cell is configured by sandwiching an electrolyte material between a fuel electrode (minus electrode) and an air electrode (plus electrode), and the type can be classified according to the type of the electrolyte material.
JP 2004-330181 A JP 2003-342584 A

リン酸型燃料電池及び高分子電解質形燃料電池では、燃料極（マイナス極）及び空気極（プラス極）として白金系の触媒が使用され、これが燃料電池の価格を高くする原因となっている。例えば、自動車１台に要求される電力を１００ｋＷとすると、自動車１台あたりに必要な白金の価格は３０万円程度と言われている。
本発明は、上記の背景に鑑みてなされたものであり、安価で比較的高い発電効率を提供することができる燃料電池、それに好適な触媒及びその製造方法を目的とする。 In phosphoric acid fuel cells and polymer electrolyte fuel cells, platinum-based catalysts are used as the fuel electrode (minus electrode) and the air electrode (plus electrode), which causes the fuel cell price to increase. For example, if the electric power required for one car is 100 kW, the price of platinum required for one car is said to be about 300,000 yen.
The present invention has been made in view of the above-described background, and an object of the present invention is to provide a fuel cell capable of providing relatively high power generation efficiency at a low cost, a catalyst suitable for the fuel cell, and a method for manufacturing the same.

本発明の第１の側面は、燃料電池用触媒に係り、該燃料電池用触媒は、酵母の少なくとも一部分の炭化物を含む。前記酵母の少なくとも一部分は、酵母の細胞壁を含みうる。前記燃料電池用触媒は、ビール糟の炭化物を更に含んでもよい。前記燃料電池用触媒は、前記炭化物に白金微粒子を担持させてなることが好ましい。   A first aspect of the present invention relates to a fuel cell catalyst, which includes at least a part of a carbide of yeast. At least a portion of the yeast may comprise a yeast cell wall. The fuel cell catalyst may further include beer bran carbide. The fuel cell catalyst is preferably formed by supporting platinum fine particles on the carbide.

本発明の第２の側面は、燃料電池に係り、該燃料電池は、電解質物質を燃料極及び空気極で挟んで構成され、前記燃料極及び前記空気極が酵母の少なくとも一部分の炭化物を含む。   A second aspect of the present invention relates to a fuel cell, and the fuel cell is configured by sandwiching an electrolyte substance between a fuel electrode and an air electrode, and the fuel electrode and the air electrode include a carbide of at least a part of yeast.

本発明の第３の側面は、炭化物を含む燃料電池用触媒の製造方法に係り、該方法は、酵母の少なくとも一部分を高圧成形して固形体を形成し、該固形体を乾留により炭化させることを含む。   A third aspect of the present invention relates to a method for producing a catalyst for a fuel cell containing a carbide, wherein the method forms a solid body by high-pressure molding at least a part of yeast, and carbonizes the solid body by dry distillation. including.

本発明の第４の側面は、炭化物を含む燃料電池用触媒の製造方法に係り、該方法は、酵母の少なくとも一部分を高圧成形して固形体を形成し、該固形体を乾留により炭化させて炭化物を得て、該炭化物に白金微粒子を担持させることを含む。   According to a fourth aspect of the present invention, there is provided a method for producing a catalyst for a fuel cell containing a carbide, wherein at least a part of yeast is subjected to high pressure molding to form a solid, and the solid is carbonized by dry distillation. Including obtaining carbide and supporting platinum fine particles on the carbide.

本発明によれば、安価で比較的高い発電効率を提供することができる燃料電池、それに好適な触媒及びその製造方法が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the fuel cell which can provide comparatively high electric power generation efficiency cheaply, the catalyst suitable for it, and its manufacturing method are provided.

以下、添付図面を参照しながら本発明の好適な実施形態を説明する。   Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings.

図１は、本発明の好適な実施形態の燃料電池の概略構成を示す図である。本発明の好適な実施形態の燃料電池１００は、水素イオンを通す電解質物質３０を燃料極１０と空気極２０とで挟んで構成される。電解質物質３０としてリン酸を含む電解質物質を使用する燃料電池は、リン酸形燃料電池と呼ばれる。電解質物質３０として高分子電解質物質（高分子イオン交換膜）を使用する燃料電池は、高分子電解質形燃料電池（ＰＥＦＣ）と呼ばれる。   FIG. 1 is a diagram showing a schematic configuration of a fuel cell according to a preferred embodiment of the present invention. A fuel cell 100 according to a preferred embodiment of the present invention is configured by sandwiching an electrolyte material 30 through which hydrogen ions pass between a fuel electrode 10 and an air electrode 20. A fuel cell that uses an electrolyte material containing phosphoric acid as the electrolyte material 30 is called a phosphoric acid fuel cell. A fuel cell that uses a polymer electrolyte material (polymer ion exchange membrane) as the electrolyte material 30 is called a polymer electrolyte fuel cell (PEFC).

燃料極１０は、酵母の少なくとも一部分を炭化させた炭化物で構成された多孔質導電性物質に白金微粒子（粒子径は、例えば２〜５ｎｍ）を担持させた燃料極触媒層１２を含む。燃料極１０は、必要に応じて、燃料極触媒層１２を支持する多孔質導電性支持層１１を含みうる。   The fuel electrode 10 includes a fuel electrode catalyst layer 12 in which platinum fine particles (particle diameter is, for example, 2 to 5 nm) are supported on a porous conductive material made of a carbide obtained by carbonizing at least a part of yeast. The fuel electrode 10 may include a porous conductive support layer 11 that supports the fuel electrode catalyst layer 12 as necessary.

空気極２０は、酵母の少なくとも一部分を炭化させた炭化物で構成された多孔質導電性物質に白金微粒子（粒子径は、例えば２〜５ｎｍ）を担持させた空気極触媒層２２を含む。空気極２０は、必要に応じて、空気触媒層２２を支持する多孔質導電性支持層２１を含みうる。   The air electrode 20 includes an air electrode catalyst layer 22 in which platinum fine particles (particle diameter is, for example, 2 to 5 nm) are supported on a porous conductive material made of a carbide obtained by carbonizing at least a part of yeast. The air electrode 20 may include a porous conductive support layer 21 that supports the air catalyst layer 22 as necessary.

燃料極１０に水素を供給し、空気極２０に酸素を供給すると、燃料極触媒層１２において水素が電子を放出して水素イオンとなる。電子は、負荷（電気回路）４０を通して空気極２０に移動する。水素イオンは、電解質物質３０中を空気極２０に向かって移動し、空気極２０において、酸素、及び、負荷４０を通して移動してくる電子と結合して水を生成する。   When hydrogen is supplied to the fuel electrode 10 and oxygen is supplied to the air electrode 20, the hydrogen releases electrons in the fuel electrode catalyst layer 12 to become hydrogen ions. The electrons move to the cathode 20 through a load (electric circuit) 40. The hydrogen ions move in the electrolyte substance 30 toward the air electrode 20, and combine with oxygen and electrons moving through the load 40 in the air electrode 20 to generate water.

この実施形態では、触媒層１２、２２の材料である炭化物（以下、材料炭化物）は、酵母の少なくとも一部分を炭化して構成される。ここで、酵母の一部分は、酵母の細胞壁を含みうる。酵母の細胞壁は、酵母から酵母エキスを搾り出した後に残る部分である。   In this embodiment, the carbide (hereinafter, “material carbide”) that is a material of the catalyst layers 12 and 22 is configured by carbonizing at least a part of yeast. Here, the portion of the yeast may include the yeast cell wall. The cell wall of yeast is a portion that remains after squeezing yeast extract from yeast.

材料炭化物は、例えば、酵母の少なくとも一部分を高圧で成型して固形体を形成し、次いで、該固形体を乾留（部分燃焼を含む）させて炭化することによって製造されうる。炭化物の製造方法については、例えば、特開２００３−３４２５８４号公報、特開平０１−１１２９７２号公報、特開平２−２９４３９１号公報、特開２０００−２４０８６４号公報等に記載されている。   The material carbide can be produced, for example, by molding at least a part of yeast at high pressure to form a solid body, and then carbonizing the solid body by dry distillation (including partial combustion). About the manufacturing method of the carbide | carbonized_material, it describes in Unexamined-Japanese-Patent No. 2003-342584, Unexamined-Japanese-Patent No. 01-112972, Unexamined-Japanese-Patent No. 2-294391, Unexamined-Japanese-Patent No. 2000-240864 etc., for example.

図２は、本発明の好適な実施形態の材料炭化物の特性（評価結果）を示すグラフである。図２における横軸は、標準水素電極（ＮＨＥ）を基準電極とする電位であり、図２における縦軸は、電極断面積あたりの電流値である。図２の示す特性は、酸素飽和水溶液を電解液として回転ディスク電極法にしたがって材料炭化物を評価した結果である。   FIG. 2 is a graph showing characteristics (evaluation results) of material carbide according to a preferred embodiment of the present invention. The horizontal axis in FIG. 2 is a potential with a standard hydrogen electrode (NHE) as a reference electrode, and the vertical axis in FIG. 2 is a current value per electrode cross-sectional area. The characteristics shown in FIG. 2 are the results of evaluating the material carbide according to the rotating disk electrode method using an oxygen saturated aqueous solution as the electrolyte.

回転ディスク電極法は、ディスク状の電極を高速で回転させることによって電極表面に層流を形成し、反応体の拡散供給を一定にしつつ、電流−電圧曲線（ボルタモグラム）を測定する手法である。   The rotating disk electrode method is a method in which a laminar flow is formed on the surface of an electrode by rotating a disk-shaped electrode at a high speed, and a current-voltage curve (voltammogram) is measured while the diffusion supply of reactants is made constant.

図２において、「ＸＣ７２」は、比較例として挙げたものであり、Ｃａｒｂｏｔ社のファーネスブラックＸＣ−７２Ｒである。「ＸＣ７２」は燃料電池触媒の白金担体として広く用いられている標準的なカーボンブラックである。また、「ＹＳＴ」は、酵母を炭化させて得られる材料炭化物であり、「ＹＣＷ」は、酵母の細胞壁を炭化させて得られる材料炭化物であり、「８０ＢＥＧ−２０ＹＳＴ」は、８０％がビール糟、２０％が酵母で構成される原料を炭化させて得られる材料炭化物である。   In FIG. 2, “XC72” is given as a comparative example and is a furnace black XC-72R manufactured by Carbot. “XC72” is a standard carbon black widely used as a platinum carrier for fuel cell catalysts. “YST” is a material carbide obtained by carbonizing yeast, “YCW” is a material carbide obtained by carbonizing the cell wall of yeast, and “80BEG-20YST” is 80% of beer lees. , 20% is a material carbide obtained by carbonizing a raw material composed of yeast.

図２において、電流が流れ始めるポイントにおける電位が大きいほど特性が優れている。注目すべきは、現在の燃料電池における標準的な材料炭化物である「ＸＣ７２」よりも、本発明の好適な実施形態における「ＹＣＷ」、「８０ＢＥＧ−２０ＹＳＴ」、「ＹＳＴ」の方が優れた特性を示していることである。「ＹＣＷ」、「８０ＢＥＧ−２０ＹＳＴ」、「ＹＳＴ」は、材料の時点で「ＸＣ７２」よりも優れた特性を有しているため、より少ない白金微粒子の担持量で「ＸＣ７２」に白金微粒子を担持させたものと同等の性能を達成することができる。   In FIG. 2, the larger the potential at the point where current starts to flow, the better the characteristics. It should be noted that “YCW”, “80BEG-20YST” and “YST” in the preferred embodiment of the present invention are superior to “XC72” which is a standard material carbide in current fuel cells. It is to show. “YCW”, “80BEG-20YST”, and “YST” have characteristics superior to “XC72” at the time of material, so platinum particles are supported on “XC72” with a smaller amount of supported platinum particles. A performance equivalent to that obtained can be achieved.

よって、「ＹＣＷ」、「８０ＢＥＧ−２０ＹＳＴ」、「ＹＳＴ」等のように酵母の少なくとも一部分を炭化させた炭化物を材料炭化物として使用することにより、「ＸＣ７２」に白金微粒子を担持させた触媒層と同等の性能を有する触媒層を得るために要する白金微粒子の量を減らすことができる。したがって、この実施形態のように、酵母の少なくとも一部分を炭化させて材料炭化物を得ることによって、安価で比較的高い発電効率を提供することができる燃料電池用触媒及びそれを有する燃料電池を得ることができる。   Therefore, by using a carbide obtained by carbonizing at least a part of yeast, such as “YCW”, “80BEG-20YST”, “YST”, etc., as a material carbide, The amount of platinum fine particles required for obtaining a catalyst layer having equivalent performance can be reduced. Therefore, as in this embodiment, by obtaining carbonized material by carbonizing at least a part of yeast, a fuel cell catalyst capable of providing a relatively high power generation efficiency at low cost and a fuel cell having the same are obtained. Can do.

燃料電池での反応に関与する電子数は２、あるいは４である。２の場合の生成物は過酸化水素、４の場合の生成物は水である。電極の劣化を防ぐ観点から４の場合の反応が望ましい。二つの還元反応が同時におこる場合、反応関与電子数は、２と４の間にある。「８０ＢＥＧ−２０ＹＳＴ」及び「ＹＳＴ」については３．５、「ＹＳＴ」については３．４である。数値が４に近いということは、より望ましい反応の比率が高いことを意味する。   The number of electrons involved in the reaction in the fuel cell is 2 or 4. The product in case 2 is hydrogen peroxide and the product in case 4 is water. The reaction in the case of 4 is desirable from the viewpoint of preventing electrode deterioration. When two reduction reactions occur simultaneously, the number of reaction participating electrons is between 2 and 4. “80BEG-20YST” and “YST” are 3.5, and “YST” is 3.4. A numerical value close to 4 means that the ratio of more desirable reactions is high.

本発明の好適な実施形態の燃料電池の概略構成を示す図である。It is a figure which shows schematic structure of the fuel cell of suitable embodiment of this invention. 本発明の好適な実施形態の材料炭化物の特性（評価結果）を示すグラフである。It is a graph which shows the characteristic (evaluation result) of the material carbide | carbonized_material of suitable embodiment of this invention.

符号の説明Explanation of symbols

１０ 燃料極
１１ 多孔質導電性支持層
１２ 燃料極触媒層
２０ 空気極
２１ 多孔質導電性支持層
２２ 空気極触媒層
１００ 燃料電池 DESCRIPTION OF SYMBOLS 10 Fuel electrode 11 Porous electroconductive support layer 12 Fuel electrode catalyst layer 20 Air electrode 21 Porous electroconductive support layer 22 Air electrode catalyst layer 100 Fuel cell

Claims (7)

酵母の少なくとも一部分の炭化物を含むことを特徴とする燃料電池用触媒。   A fuel cell catalyst comprising a carbide of at least a portion of yeast. 前記酵母の少なくとも一部分が酵母の細胞壁を含むことを特徴とする請求項１に記載の燃料電池用触媒。   The fuel cell catalyst according to claim 1, wherein at least a part of the yeast contains a cell wall of yeast. ビール糟の炭化物を更に含むことを特徴とする請求項１に記載の燃料電池用触媒。   The fuel cell catalyst according to claim 1, further comprising carbide of beer lees. 前記炭化物に白金微粒子を担持させてなることを特徴とする請求項１乃至３のいずれか１項に記載の燃料電池用触媒。   The fuel cell catalyst according to any one of claims 1 to 3, wherein platinum fine particles are supported on the carbide. 電解質物質を燃料極及び空気極で挟んで構成される燃料電池であって、
前記燃料極及び前記空気極が酵母の少なくとも一部分の炭化物を含むことを特徴とする燃料電池。 A fuel cell configured by sandwiching an electrolyte substance between a fuel electrode and an air electrode,
The fuel cell, wherein the fuel electrode and the air electrode contain a carbide of at least a part of yeast. 炭化物を含む燃料電池用触媒の製造方法であって、
酵母の少なくとも一部分を高圧成形して固形体を形成し、該固形体を乾留により炭化させることを特徴とする燃料電池用触媒の製造方法。 A method for producing a fuel cell catalyst containing a carbide,
A method for producing a fuel cell catalyst, comprising: forming a solid body by high-pressure molding at least a part of yeast; and carbonizing the solid body by dry distillation. 炭化物を含む燃料電池用触媒の製造方法であって、
酵母の少なくとも一部分を高圧成形して固形体を形成し、該固形体を乾留により炭化させて炭化物を得て、該炭化物に白金微粒子を担持させることを特徴とする燃料電池用触媒の製造方法。 A method for producing a fuel cell catalyst containing a carbide,
A method for producing a catalyst for a fuel cell, comprising forming a solid body by high-pressure molding at least a part of yeast, carbonizing the solid body by dry distillation to obtain a carbide, and supporting the platinum fine particles on the carbide.
JP2006114977A 2006-04-18 2006-04-18 Catalyst for fuel cell, fuel cell, and method for producing catalyst for fuel cell Expired - Fee Related JP4915840B2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091020A1 (en) * 2003-04-08 2004-10-21 Matsushita Electric Industrial Co. Ltd. Electrode for oxygen reduction and electrochemical device using the same
JP2004335282A (en) * 2003-05-08 2004-11-25 Sony Corp Catalyst, catalyst electrode and manufacturing method of the same, membrane-electrode assembly, and electrochemical device
WO2005099009A1 (en) * 2004-04-06 2005-10-20 Matsushita Electric Industrial Co., Ltd. Electrode and fuel cell
JP2005339962A (en) * 2004-05-26 2005-12-08 Matsushita Electric Ind Co Ltd Polymer membrane electrode jointed body, polymer electrolyte fuel cell and manufacturing method for polymer membrane electrode jointed body

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004091020A1 (en) * 2003-04-08 2004-10-21 Matsushita Electric Industrial Co. Ltd. Electrode for oxygen reduction and electrochemical device using the same
JP2004335282A (en) * 2003-05-08 2004-11-25 Sony Corp Catalyst, catalyst electrode and manufacturing method of the same, membrane-electrode assembly, and electrochemical device
WO2005099009A1 (en) * 2004-04-06 2005-10-20 Matsushita Electric Industrial Co., Ltd. Electrode and fuel cell
JP2005339962A (en) * 2004-05-26 2005-12-08 Matsushita Electric Ind Co Ltd Polymer membrane electrode jointed body, polymer electrolyte fuel cell and manufacturing method for polymer membrane electrode jointed body

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