JPS61165966A - Regeneration of fuel electrode of fuel cell - Google Patents

Regeneration of fuel electrode of fuel cell

Info

Publication number
JPS61165966A
JPS61165966A JP60006171A JP617185A JPS61165966A JP S61165966 A JPS61165966 A JP S61165966A JP 60006171 A JP60006171 A JP 60006171A JP 617185 A JP617185 A JP 617185A JP S61165966 A JPS61165966 A JP S61165966A
Authority
JP
Japan
Prior art keywords
gas
fuel
supply
pure hydrogen
hydrogen gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP60006171A
Other languages
Japanese (ja)
Inventor
Masato Nishioka
正人 西岡
Yasuo Miyake
泰夫 三宅
Yasuhiko Ito
靖彦 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Priority to JP60006171A priority Critical patent/JPS61165966A/en
Publication of JPS61165966A publication Critical patent/JPS61165966A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
    • 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

Abstract

PURPOSE:To revitalize catalyst of a fuel electrode poisoned by carbon monoxide by switching a system to supply of pure hydrogen gas, as soon as stopping supply of fuel gas before applying nitrogen purge and performing discharge for a predetermined time. CONSTITUTION:Supply of fuel gas is stopped by closing a valve 7 before applying nitrogen purge and concurrently the supplying system is switched to supply of pure hydrogen gas from a bomb 12. In this case, discharging is continued for about 1hr by utilizing air and pure hydrogen gas without stopping supply of the air. Because adsorption equilibrium is shifted to the H2 side during the discharging period, the surface of platinum can be vitalized by removing the Co adsorbed on the platinum catalyst.

Description

【発明の詳細な説明】 （イ）産業上の利用分野 本発明は燃料電池における燃料極の再生方法に係り、特
に燃料ガス中の一酸化炭素により被毒された触媒を再活
性化する方法に関するものであろう（ロ）従来の技術 一般に燃料電池の燃料極に供給される燃料ガスとして、
燃料処理装置（リフオーマ及びシフトコンバータ）で改
質・転化された水素リッチガスか用いられる。この水素
リヅチガスの組成比は電池負荷の変動などに応じて多少
変化するがＨ２約８０％、ＣＯ２約２０％、ＣＯ約０．
５％であり、この成分中ＣＯ２は不活性であるため単に
燃料ガスの水素分圧を下げるだけであるが、ＣＯに関し
てはそのわづかの濃度でさえも白金などの触媒を被毒す
る。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a method for regenerating a fuel electrode in a fuel cell, and particularly relates to a method for reactivating a catalyst poisoned by carbon monoxide in fuel gas. (b) Conventional technology In general, as fuel gas supplied to the fuel electrode of a fuel cell,
Hydrogen-rich gas that has been reformed and converted in a fuel processing device (reformer and shift converter) is used. The composition ratio of this hydrogen rich gas varies somewhat depending on changes in battery load, etc., but it is about 80% H2, about 20% CO2, and about 0% CO2.
5%, and since CO2 in this component is inert, it simply lowers the hydrogen partial pressure of the fuel gas, but even a small concentration of CO poisons catalysts such as platinum.

燃料電池の長期作動中、このような−酸化炭素下をもた
らすという問題があった。During long-term operation of fuel cells, there is a problem in that such carbon oxide conditions occur.

（ハ）発明が解決しようとする問題点 この発明は一酸化炭素により被毒した燃料極の触媒を再
活性化して前記問題点を解決するものである。(c) Problems to be Solved by the Invention This invention solves the above-mentioned problems by reactivating the catalyst in the fuel electrode that has been poisoned by carbon monoxide.

に）問題点を解決するための手段 この発明は電池のシャットダウンに際し、周知の窒素％
に一ジを行う前に、燃料ガスの供給を停止すると同時に
純水素ガスの供給に切り替えて所定時間放電を行うもの
である。2) Means for Solving Problems This invention provides a solution to the well-known nitrogen percentage during battery shutdown.
Before performing the first cycle, the supply of fuel gas is stopped, and at the same time, the supply of pure hydrogen gas is switched to the supply of pure hydrogen gas, and discharge is performed for a predetermined period of time.

（ホ）作用 この発明では触媒上に吸着しているＧＯは、純水素ガス
で放電することにより、吸着平衡がＨ２側にずらされる
ために取除かれ、ＣＯが除去された触媒上でＨ２の酸化
を行って触媒表面を再活性化する。(E) Effect In this invention, the GO adsorbed on the catalyst is removed by discharging with pure hydrogen gas, as the adsorption equilibrium is shifted to the H2 side, and the H2 is removed on the catalyst from which CO has been removed. Oxidation is performed to reactivate the catalyst surface.

（へ）実施例 電池スタック（１）は単位セルとガス分離板とを交互に
多数積重し、数セル毎に冷却板を介在させて構成される
が、第１図は空気極と燃料極の各供給ガス室（Ｐ）（へ
）及び冷却ガス通路（ｑをもつ模型図として示されてい
る。(f) Example Battery stack (1) is constructed by stacking a large number of unit cells and gas separation plates alternately, with a cooling plate interposed between every few cells. Each of the supply gas chambers (P) and cooling gas passages (q) are shown as schematic diagrams.

燃料処理装置（２）は、スチームリフオーマ（３）とシ
フトコンバータ（４）で構成され、天然ガス・メタンな
どの燃料を改質して後改質ガス中の一酸化炭素を二酸化
炭素に転化する。The fuel processing device (2) consists of a steam reformer (3) and a shift converter (4), which reformes fuel such as natural gas or methane and converts carbon monoxide in the reformed gas into carbon dioxide. do.

得られた燃料ガスは燃料極ガス室（財）へ供給され、空
気極ガス室ｒ）に供給された空気との間で電池反応が行
われる。電池反応により昇温する電池スタック（１）は
、熱交換器（５）及びブロワ（６）を経て通路ｑに流れ
る循環冷却ガスで冷却され、１８０〜１９０度の作動温
度に維持される。The obtained fuel gas is supplied to the fuel electrode gas chamber (F), and a cell reaction is performed with the air supplied to the cathode gas chamber (r). The battery stack (1), whose temperature rises due to battery reaction, is cooled by circulating cooling gas flowing through the passage q through the heat exchanger (5) and the blower (6), and is maintained at an operating temperature of 180 to 190 degrees.

がＣＯで被毒され、触媒能が劣化して作動電圧の低下を
もたらす。is poisoned by CO, deteriorating its catalytic ability and causing a drop in operating voltage.

第２図の特性図には、燃料ガス中のＣＯ濃度（至）と作
動電圧低下との関係が電池作動温度をパラメータとして
示されているう 一般に電池のシャットダウン時には供給バルブ（７）（
８）を閉じて両反応ガスの供給を停止し、ついでバルブ
（９）ααを開いて窒素ガスをガス室（Ｐ）Ｈに供給し
、反応ガスを窒素ガスで置換する窒素パージを行って後
休止状態に入る。The characteristic diagram in Figure 2 shows the relationship between the CO concentration in the fuel gas (maximum) and the operating voltage drop using the battery operating temperature as a parameter.Generally, when the battery is shut down, the supply valve (7)
8) to stop the supply of both reaction gases, then open the valve (9) αα to supply nitrogen gas to the gas chamber (P)H, and perform a nitrogen purge to replace the reaction gas with nitrogen gas. Enter hibernation.

本発明ではこの窒素パージに先立ち、バルブ（７）を閉
じて燃料ガスの供給を停止すると同時にバルブ圓を開い
てボンベ■からの純水素ガスの供給に切り替える。この
際空気の供給は停止することなく空気と純水素ガスによ
り約１時間放電（放風電流１０〜２０　ｍＡ／ｄ　）を
行う。この放電期間中吸着平衡がＨ２側にずらされるの
で、白金触媒上に吸着しているＣＯは取り除かれて白金
表面を活性化する。このような純水素による放電終了後
、周知のように窒素パージを行う。In the present invention, prior to this nitrogen purge, the valve (7) is closed to stop the supply of fuel gas, and at the same time, the valve ring is opened to switch to the supply of pure hydrogen gas from the cylinder (2). At this time, the air supply is not stopped, and discharge is performed using air and pure hydrogen gas for about 1 hour (air discharge current: 10 to 20 mA/d). During this discharge period, the adsorption equilibrium is shifted to the H2 side, so that the CO adsorbed on the platinum catalyst is removed and the platinum surface is activated. After the discharge with pure hydrogen is completed, nitrogen purge is performed as is well known.

以上実施例は白金触媒の場合について説明したが本発明
法は白金族触媒は勿論燃料極に用いられる触媒のすべて
について適用可能である。Although the above embodiments have been described using platinum catalysts, the method of the present invention is applicable to all catalysts used in fuel electrodes, as well as platinum group catalysts.

（ト）効果 本発明によれば、燃料ガス中の一酸化炭素により被毒さ
れた触媒は、電池のシャットダウン時窒素パージに先立
って、純水素による放電を行うことにより再生され、電
池の再作動時作動電圧及び燃料利用率の低下を補償して
電池寿命を伸ばすことができる。(G) Effects According to the present invention, the catalyst poisoned by carbon monoxide in the fuel gas is regenerated by discharging with pure hydrogen prior to nitrogen purge during battery shutdown, and the battery is restarted. The battery life can be extended by compensating for the decrease in operating voltage and fuel utilization.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明方法を説明するための燃料電池システム
のプロヅク図、第２図は燃料ガス中のＧＯ濃度と作動電
圧低下との関係を示す特性図であるっ（１）・・・電池
スタック、（ト）・・・空気極ガス室、（へ）・・・燃
料極ガス室、ｑ・・・冷却ガス通路、（２）・・・燃料
処理装置ｔ、（３１・・・リフオーマ−１（４）・・・
シフトコンバータ、（７＋　、　（８１・・・反応ガス
供給バルブ、αＤ・・・純水素供給バルブ。Fig. 1 is a project diagram of a fuel cell system for explaining the method of the present invention, and Fig. 2 is a characteristic diagram showing the relationship between GO concentration in fuel gas and operating voltage drop.(1)...Battery Stack, (g)... Air electrode gas chamber, (f)... Fuel electrode gas chamber, q... Cooling gas passage, (2)... Fuel processing device t, (31... Reformer) 1 (4)...
Shift converter, (7+, (81... Reaction gas supply valve, αD... Pure hydrogen supply valve.

Claims (1)

【特許請求の範囲】[Claims] （１）燃料ガスとして燃料処理装置で改質・転化された
水素リッチガスを用い、酸化ガスとして空気を用いる燃
料電池において、前記電池のシャットダウンに際し、窒
素パージを行うに先立ち前記燃料ガスの供給を停止する
と同時に純水素ガスの供給に切り替え、前記純水素ガス
と空気による所定期間の放電を行うことにより、触媒に
吸着している一酸化炭素を除去せしめることを特徴とす
る燃料電池燃料極の再生方法。(1) In a fuel cell that uses hydrogen-rich gas reformed and converted by a fuel processing device as the fuel gas and air as the oxidizing gas, when shutting down the cell, the supply of the fuel gas is stopped before nitrogen purge is performed. At the same time, the supply of pure hydrogen gas is switched to, and carbon monoxide adsorbed on the catalyst is removed by discharging the pure hydrogen gas and air for a predetermined period. .
JP60006171A 1985-01-17 1985-01-17 Regeneration of fuel electrode of fuel cell Pending JPS61165966A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60006171A JPS61165966A (en) 1985-01-17 1985-01-17 Regeneration of fuel electrode of fuel cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60006171A JPS61165966A (en) 1985-01-17 1985-01-17 Regeneration of fuel electrode of fuel cell

Publications (1)

Publication Number Publication Date
JPS61165966A true JPS61165966A (en) 1986-07-26

Family

ID=11631098

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60006171A Pending JPS61165966A (en) 1985-01-17 1985-01-17 Regeneration of fuel electrode of fuel cell

Country Status (1)

Country Link
JP (1) JPS61165966A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2290409A (en) * 1994-06-16 1995-12-20 British Gas Plc Operation of fuel cell wherein poisoned anode catalyst is intermittently rejuvenated by applying a DC potential
KR100717747B1 (en) 2005-10-25 2007-05-11 삼성에스디아이 주식회사 Method of recovering stack for direct oxidation fuel cell
WO2007063783A1 (en) * 2005-11-30 2007-06-07 Toyota Jidosha Kabushiki Kaisha Fuel cell system
JP2011151043A (en) * 1999-09-27 2011-08-04 Bdf Ip Holdings Ltd Method for improving cold starting capability of electrochemical fuel cell

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2290409A (en) * 1994-06-16 1995-12-20 British Gas Plc Operation of fuel cell wherein poisoned anode catalyst is intermittently rejuvenated by applying a DC potential
US5601936A (en) * 1994-06-16 1997-02-11 British Gas Plc Method of operating a fuel cell
GB2290409B (en) * 1994-06-16 1997-04-02 British Gas Plc A method of operating a fuel cell
JP2011151043A (en) * 1999-09-27 2011-08-04 Bdf Ip Holdings Ltd Method for improving cold starting capability of electrochemical fuel cell
KR100717747B1 (en) 2005-10-25 2007-05-11 삼성에스디아이 주식회사 Method of recovering stack for direct oxidation fuel cell
WO2007063783A1 (en) * 2005-11-30 2007-06-07 Toyota Jidosha Kabushiki Kaisha Fuel cell system
US8288050B2 (en) 2005-11-30 2012-10-16 Toyota Jidosha Kabushiki Kaisha Fuel cell system

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