JP2006073351A - Gas cross leakage detection method - Google Patents

Gas cross leakage detection method Download PDF

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JP2006073351A
JP2006073351A JP2004255338A JP2004255338A JP2006073351A JP 2006073351 A JP2006073351 A JP 2006073351A JP 2004255338 A JP2004255338 A JP 2004255338A JP 2004255338 A JP2004255338 A JP 2004255338A JP 2006073351 A JP2006073351 A JP 2006073351A
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gas
gas cross
open circuit
circuit voltage
cross leak
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Takanori Wada
崇徳 和田
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Fuji Electric Co Ltd
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Fuji Electric Holdings Ltd
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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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas cross leakage detection method capable of detecting the gas cross leakage 7 with a high precision and capable of prolonging the time when continuous operation of a fuel cell is possible without damaging a solid polyelectrolyte film 4 such as by increasing a through hole diameter of the solid polyelectrolyte film 4 and by forming a large through hole in a thin film part 1. <P>SOLUTION: An open circuit voltage difference ΔV (=VTdc-VTdc_30) is regularly measured during the continuous operation of the fuel cell. The VTdc is the open circuit voltage when a humidified dew point temperature of an air electrode 22 is Tdc (°C), and VTdc_30 is the open circuit voltage at a humidified dew point (Tdc_30) when the humidified dew point of the air electrode 22 is reduced to 30°C. By sending a signal to show detection of the gas cross leakage 7 when it becomes ΔV≥0 (V) to a desired monitor device or the like (not illustrated), sudden reduction of output of a single cell 20 due to the gas cross leakage 7 can be detected in advance and prevented. This is similar by lowering Tdc (°C) by 10°C or more. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、燃料極と空気極とにより固体高分子電解質膜を挟持した固体高分子形燃料電池における当該固体高分子電解質膜間のガスクロスリーク検知方法に関する。   The present invention relates to a gas cross leak detection method between solid polymer electrolyte membranes in a solid polymer electrolyte fuel cell in which a solid polymer electrolyte membrane is sandwiched between a fuel electrode and an air electrode.

近年、固体高分子形燃料電池（固体電解質形燃料電池。Polymer Electrolyte Fuel Cell : ＰＥＦＣ）の開発が進められている。固体高分子形燃料電池の発電の仕組みは基本的に他の燃料電池と同様であり、反応ガス中の水素と酸素とから水を生成する反応を利用して発電が行なわれている。   In recent years, solid polymer fuel cells (polymer electrolyte fuel cells: PEFC) have been developed. The power generation mechanism of the polymer electrolyte fuel cell is basically the same as that of other fuel cells, and power generation is performed using a reaction that generates water from hydrogen and oxygen in the reaction gas.

図４は、固体高分子形燃料電池の最小単位である単電池（単セル）２０の電極構造（断面図）を示す。図４に示されるように単セル２０は、中央部の固体高分子電解質膜４を、燃料極触媒層３ａおよびその上部に形成された燃料極（ガス）拡散層２ａからなる燃料極２１と、空気極触媒層３ｂおよびその下部に形成された空気極（ガス）拡散層２ｂからなる空気極２２とにより挟持されて構成されている。燃料極２１の外側には燃料である水素のガス流通部８ａを有するセパレータ５ａが燃料極拡散層２ａに面接され、空気極２２の外側には空気のガス流通部８ｂを有するセパレータ５ｂが空気極拡散層２ｂに面接されている。固体高分子電解質膜４とセパレータ５ａおよび５ｂとの間には、各々燃料極拡散層２ａおよび空気極拡散層２ｂを囲むガスシール部６が配置されている。図４において、符号９は単セル２０のセル電圧を測定する電圧計、１（点線で囲まれた部分）は固体高分子電解質膜４中に生じた電解質膜亀裂部または薄膜部、７は電解質膜亀裂部または薄膜部１を透過する水素（ガスクロスリーク）である。電解質膜亀裂部または薄膜部１としたのは、ガスクロスリーク７は、固体高分子電解質膜４中に亀裂部がなくても水素の透過性の高さにより極微量ながら薄膜部を通して生じるためである。実際に発電装置として燃料電池を適用する場合には、単セル２０を何セルか積層して燃料電池スタック１２（後述）を構成して発電するのが一般的である。   FIG. 4 shows an electrode structure (cross-sectional view) of a unit cell (unit cell) 20 which is the minimum unit of the polymer electrolyte fuel cell. As shown in FIG. 4, the unit cell 20 includes a solid polymer electrolyte membrane 4 in a central portion, a fuel electrode 21 including a fuel electrode catalyst layer 3 a and a fuel electrode (gas) diffusion layer 2 a formed thereon, The air electrode catalyst layer 3b and an air electrode 22 composed of an air electrode (gas) diffusion layer 2b formed under the air electrode catalyst layer 3b are sandwiched between the air electrode catalyst layer 3b and the air electrode 22. A separator 5a having a hydrogen gas circulation part 8a serving as fuel is in contact with the fuel electrode diffusion layer 2a outside the fuel electrode 21, and a separator 5b having an air gas circulation part 8b is outside the air electrode 22 at the air electrode. It is in contact with the diffusion layer 2b. Between the solid polymer electrolyte membrane 4 and the separators 5a and 5b, gas seal portions 6 surrounding the fuel electrode diffusion layer 2a and the air electrode diffusion layer 2b are disposed. In FIG. 4, reference numeral 9 denotes a voltmeter for measuring the cell voltage of the single cell 20, 1 (portion surrounded by a dotted line) denotes an electrolyte membrane crack or thin film portion generated in the solid polymer electrolyte membrane 4, and 7 denotes an electrolyte. It is hydrogen (gas cross leak) that permeates through the film crack part or the thin film part 1. The reason why the electrolyte membrane crack portion or the thin film portion 1 is used is that the gas cross leak 7 occurs through the thin film portion with a very small amount of hydrogen due to its high hydrogen permeability even if there is no crack portion in the solid polymer electrolyte membrane 4. . When a fuel cell is actually applied as a power generation device, it is general to generate power by stacking several single cells 20 to form a fuel cell stack 12 (described later).

図５は、従来の固体高分子形燃料電池の単セル２０を積層した燃料電池スタック１２へのガス供給方法を説明するための図である。図５に示されるように、燃料電池スタック１２の内部にある燃料極２１（図５中では不図示）へは、水素、または原燃料の都市ガスを改質器１０にて水蒸気改質して生成した水素を含むガスを、燃料ガス２５として供給する。燃料電池スタック１２の内部にある空気極２２（図５中では不図示）へは、酸素または大気中の空気２６を供給する。燃料ガス２５の水素は燃料極２１で水素イオンと電子とに分かれ、この水素イオンが固体高分子電解質膜４内を移動（透過）する際に、電気浸透により燃料極２１から空気極２２へ水を持ち去る。このため、固体高分子電解質膜４および燃料極触媒層３ａが乾燥しやすくなり、電気抵抗の増大によって電圧計９’等で測定される燃料電池の出力の低下を招くことになる。そこで、燃料電池の運転では、固体高分子電解質膜４および燃料極触媒層３ａ中の電解質皮膜を湿潤状態に保つことにより、高いセル電圧を得ている。一方、空気極２２から燃料極２１へは水の逆拡散も生じている。このため、供給ガス（燃料ガス２５および空気２６）中には適度な水蒸気を混合させて、燃料極２１および空気極２２に各々ガスを供給することが望ましい。上述のように、燃料極２１へ供給される燃料ガス２５は、原燃料である都市ガスに水蒸気が加えられ、改質器１０により水素を含むように改質されており、その時の未反応水蒸気によって燃料極２１側は加湿されている。図５に示されるように、燃料極２１側について更に加湿が必要な場合は、燃料電池スタック１２の燃料極２１の手前に燃料極加湿器１０（図５では燃料極加湿器または改質器として示す。）を設け、水素または燃料ガス２５を加湿して燃料極２１へ供給している。一方、空気極２２側については、燃料電池スタック１２の空気極２２の手前に空気極加湿器１１を設け、供給ガスである酸素または空気２６を加湿して空気極２２へ供給している。   FIG. 5 is a diagram for explaining a gas supply method to a fuel cell stack 12 in which unit cells 20 of a conventional polymer electrolyte fuel cell are stacked. As shown in FIG. 5, the fuel electrode 21 (not shown in FIG. 5) inside the fuel cell stack 12 is steam-reformed with hydrogen or raw city gas by the reformer 10. The generated hydrogen-containing gas is supplied as the fuel gas 25. Oxygen or air 26 in the atmosphere is supplied to an air electrode 22 (not shown in FIG. 5) inside the fuel cell stack 12. Hydrogen in the fuel gas 25 is separated into hydrogen ions and electrons at the fuel electrode 21, and when this hydrogen ion moves (permeates) through the solid polymer electrolyte membrane 4, water is transferred from the fuel electrode 21 to the air electrode 22 by electroosmosis. Take away. For this reason, the solid polymer electrolyte membrane 4 and the fuel electrode catalyst layer 3a are easily dried, and an increase in electric resistance causes a decrease in the output of the fuel cell measured by the voltmeter 9 'or the like. Therefore, in the operation of the fuel cell, a high cell voltage is obtained by keeping the solid polymer electrolyte membrane 4 and the electrolyte membrane in the fuel electrode catalyst layer 3a in a wet state. On the other hand, back diffusion of water also occurs from the air electrode 22 to the fuel electrode 21. For this reason, it is desirable to mix gas in the supply gas (fuel gas 25 and air 26) and supply gas to the fuel electrode 21 and the air electrode 22, respectively. As described above, the fuel gas 25 supplied to the fuel electrode 21 is reformed so that steam is added to the city gas, which is the raw fuel, and contains hydrogen by the reformer 10, and unreacted steam at that time Thus, the fuel electrode 21 side is humidified. As shown in FIG. 5, when further humidification is required on the fuel electrode 21 side, the fuel electrode humidifier 10 (in FIG. 5, as a fuel electrode humidifier or a reformer) is disposed in front of the fuel electrode 21 of the fuel cell stack 12. And hydrogen or fuel gas 25 is humidified and supplied to the fuel electrode 21. On the other hand, on the air electrode 22 side, the air electrode humidifier 11 is provided in front of the air electrode 22 of the fuel cell stack 12, and oxygen or air 26 as a supply gas is humidified and supplied to the air electrode 22.

上述の燃料電池（単セル２０）において、固体高分子電解質膜４には、電解質として水素イオンを透過させる機能と、燃料極２１および空気極２２のガスを遮断する機能とが要求される。しかし、固体高分子電解質膜４に大きな貫通孔が開いている場合、燃料極２１の水素が空気極２２へ移動してしまうことになる。あるいは、固体高分子電解質膜４に大きな貫通孔が空いていない場合であっても、固体高分子電解質膜４に薄膜部１ができた場合には、上述の水素の透過性の高さにより極微量ながら水素が燃料極２１側から空気極２２側へ移動する可能性がある。   In the above-described fuel cell (single cell 20), the solid polymer electrolyte membrane 4 is required to have a function of permeating hydrogen ions as an electrolyte and a function of blocking the gas in the fuel electrode 21 and the air electrode 22. However, when a large through hole is opened in the solid polymer electrolyte membrane 4, hydrogen in the fuel electrode 21 moves to the air electrode 22. Alternatively, even when the solid polymer electrolyte membrane 4 does not have a large through hole, when the thin film portion 1 is formed in the solid polymer electrolyte membrane 4, the above-described hydrogen permeability is extremely high. There is a possibility that hydrogen may move from the fuel electrode 21 side to the air electrode 22 side even though the amount is small.

特に、固体高分子電解質膜４に貫通孔が生じた場合には、燃料極２１から空気極２２へ大量の水素がガスクロスリークする可能性が高い。固体高分子電解質膜４に穴が開いたり、あるいは薄膜部１ができたりする原因は、連続運転状態(温度、湿度、負荷、ガス極間差圧)によるものである。燃料極２１の水素が空気極２２へ移動した場合には、空気極２２で当該水素と空気２６中の酸素が直接燃焼するため、燃料電池の出力は下がることになる。この燃焼時の熱により、更に固体高分子電解質膜４の貫通孔径が増加したり、あるいは薄膜化が進む可能性がある。従って、上述のような燃料極２１と空気極２２との間の極間ガスクロスリーク部位（ガスクロスリーク１）が生じているか否かを早期に検知する必要がある。   In particular, when a through hole is formed in the solid polymer electrolyte membrane 4, there is a high possibility that a large amount of hydrogen gas leaks from the fuel electrode 21 to the air electrode 22. The reason why the solid polymer electrolyte membrane 4 is perforated or the thin film portion 1 is formed is due to the continuous operation state (temperature, humidity, load, differential pressure between gas electrodes). When the hydrogen in the fuel electrode 21 moves to the air electrode 22, the hydrogen and oxygen in the air 26 are directly combusted in the air electrode 22, so the output of the fuel cell decreases. Due to the heat at the time of combustion, there is a possibility that the diameter of the through-hole of the solid polymer electrolyte membrane 4 is further increased or the film thickness is reduced. Therefore, it is necessary to detect at an early stage whether or not there is an inter-electrode gas cross leak portion (gas cross leak 1) between the fuel electrode 21 and the air electrode 22 as described above.

ガスクロスリーク１の検知方法としては、特許文献１に、固体高分子電解質膜をアノードとカソードで挟持してなるセルにおいて、アノードに供給する水素ガスの圧力をカソードに供給する空気の圧力よりも高く維持した状態で、開回路電圧を測定し、測定された開回路電圧が所定の電圧値以下であった場合にガスが漏れていると判定するガス漏れ検知方法が記載されている。特許文献１によれば、セルの出力電圧は、電流が流れない状態における電圧、すなわち開回路電圧で最大となる。一方、固体高分子電解質膜を水素分子が透過し、カソード側の電極付近に燃料ガスの分子が存在することにより、活性化過電圧領域における出力電圧が低下する。このことは、見かけ上、電流が流れて出力電圧が低下したのと同じ状態になる。このことから、セル電圧を測定することにより正常セルか不調セルかを判定することができ、すなわち、セルのガス漏れを検知することが可能であると記載されている。さらに、ガス漏れ検知の準備として、カソード入口圧力をアノード入口圧力よりも極わずか高くしておくことにより、このあとアノード側の圧力を高めた時の不調セルの水素透過量増大によるセル電圧の低下を顕著なものとすることができると記載されている。   As a method for detecting gas cross leak 1, in Patent Document 1, in a cell in which a solid polymer electrolyte membrane is sandwiched between an anode and a cathode, the pressure of hydrogen gas supplied to the anode is higher than the pressure of air supplied to the cathode. A gas leak detection method is described in which an open circuit voltage is measured in a maintained state, and gas is leaked when the measured open circuit voltage is equal to or lower than a predetermined voltage value. According to Patent Document 1, the output voltage of the cell becomes maximum at a voltage in a state where no current flows, that is, an open circuit voltage. On the other hand, hydrogen molecules permeate through the solid polymer electrolyte membrane, and the presence of fuel gas molecules in the vicinity of the cathode-side electrode reduces the output voltage in the activated overvoltage region. This appears to be the same state as when the output voltage drops due to current flowing. From this, it is described that it is possible to determine whether the cell is a normal cell or a malfunctioning cell by measuring the cell voltage, that is, it is possible to detect a gas leak in the cell. Furthermore, by preparing the cathode inlet pressure slightly higher than the anode inlet pressure in preparation for gas leak detection, the cell voltage decreases due to an increase in the hydrogen permeation amount of the malfunctioning cell when the anode pressure is increased thereafter. It is described that can be made remarkable.

特開２００３−４５４６６号公報JP 2003-45466 A

特許文献１記載のガス漏れ検知方法のように、アノード（燃料極２１）側の圧力を上げてカソード（空気極２２）側へ燃料ガス２５（水素）を透過させた場合、固体高分子電解質膜４の貫通孔径が増加したり、両極間の差圧により薄膜化部１に大きな貫通孔が生じてしまう可能性がある。この場合、固体高分子電解質膜４内の水素のガスクロスリーク７が加速し、燃料電池の連続運転可能な時間を短縮してしまう可能性があるという問題があった。   When the pressure on the anode (fuel electrode 21) side is increased and the fuel gas 25 (hydrogen) is permeated to the cathode (air electrode 22) side as in the gas leak detection method described in Patent Document 1, the solid polymer electrolyte membrane 4 may increase, or a large through-hole may be formed in the thinned portion 1 due to the differential pressure between the two electrodes. In this case, there is a problem that the gas cross leak 7 of hydrogen in the solid polymer electrolyte membrane 4 is accelerated and the time during which the fuel cell can be continuously operated may be shortened.

そこで、本発明の目的は、上記問題を解決するためになされたものであり、固体高分子電解質膜４の貫通孔径を増加させたり、薄膜化部１に大きな貫通孔を生じさせる等のように固体高分子電解質膜４を損傷することなくガスクロスリーク７を精度高く検知することができ、燃料電池の連続運転可能な時間を長くすることができるガスクロスリーク検知方法を提供することにある。   Accordingly, an object of the present invention is to solve the above-described problems, such as increasing the through-hole diameter of the solid polymer electrolyte membrane 4 or generating a large through-hole in the thinned portion 1. An object of the present invention is to provide a gas cross leak detection method capable of detecting the gas cross leak 7 with high accuracy without damaging the solid polymer electrolyte membrane 4 and extending the time during which the fuel cell can be continuously operated.

この発明のガスクロスリーク検知方法は、燃料極と空気極とにより固体高分子電解質膜を挟持した固体高分子形燃料電池の該固体高分子電解質膜間のガスクロスリーク検知方法であって、燃料極又は／及び空気極に供給する反応ガス中の加湿量を変えた時に測定された開回路電圧差に基づき、前記固体高分子電解質膜間のガスクロスリークを検知することを特徴とする。   A gas cross leak detection method of the present invention is a gas cross leak detection method between solid polymer electrolyte membranes of a polymer electrolyte fuel cell in which a solid polymer electrolyte membrane is sandwiched between a fuel electrode and an air electrode, the fuel electrode or And / or detecting a gas cross leak between the solid polymer electrolyte membranes based on an open circuit voltage difference measured when the amount of humidification in the reaction gas supplied to the air electrode is changed.

ここで、この発明のガスクロスリーク検知方法において、前記開回路電圧差の測定は、燃料極又は／及び空気極の加湿露点温度をＴｄｃ(℃)、Ｔｄｃ(℃)の時の開回路電圧をＶＴｄｃ(Ｖ)とし、燃料極又は／及び空気極の加湿露点をＴｄｃ(℃)からＸ℃下げた時の加湿露点をＴｄｃ_Ｘ(℃)、Ｔｄｃ_Ｘ(℃)の時の開回路電圧をＶＴｄｃ_Ｘ(Ｖ)とした場合、前記開回路電圧差としてΔＶ（Ｖ）＝ＶＴｄｃ−ＶＴｄｃ_Ｘを測定することができる。   Here, in the gas cross leak detection method of the present invention, the measurement of the open circuit voltage difference is performed by measuring the open circuit voltage when the humidification dew point temperature of the fuel electrode and / or the air electrode is Tdc (° C.) and Tdc (° C.) as VTdc. (V), and the humidification dew point when the humidification dew point of the fuel electrode or / and the air electrode is lowered by X ° C. from Tdc (° C.) is Tdc_X (° C.), and the open circuit voltage when Tdc_X (° C.) is VTdc_X (V) In this case, ΔV (V) = VTdc−VTdc_X can be measured as the open circuit voltage difference.

ここで、この発明のガスクロスリーク検知方法において、ガスクロスリークの検知は、前記固体高分子形燃料電池の連続運転中に所定の期間毎に前記開回路電圧差ΔＶ（Ｖ）を測定し、ΔＶ≧０(Ｖ)になった時にガスクロスリークを検知したものとすることができる。   Here, in the gas cross leak detection method of the present invention, the gas cross leak is detected by measuring the open circuit voltage difference ΔV (V) at predetermined intervals during continuous operation of the polymer electrolyte fuel cell, and ΔV ≧ A gas cross leak can be detected when the voltage reaches 0 (V).

ここで、この発明のガスクロスリーク検知方法において、Ｘ℃≧１０℃（好適には２０℃または３０℃）とすることができる。   Here, in the gas cross leak detection method of this invention, it can be set as X degreeC> = 10 degreeC (preferably 20 degreeC or 30 degreeC).

本発明のガスクロスリーク検知方法によれば、燃料電池の連続運転中に、定期的に開回路電圧差ΔＶを測定し、ΔＶ≧０(Ｖ)になった時に、ガスクロスリークの検知を示す信号を所望のモニタ装置等（不図示）へ送ることにより、ガスクロスリークによる単セルの出力の急低下を未然に検知し防ぐことができる。従って、固体高分子電解質膜の貫通孔径を増加させたり、薄膜化部に大きな貫通孔を生じさせる等のように固体高分子電解質膜を損傷することなくガスクロスリークを精度高く検知することができ、燃料電池の連続運転可能な時間を長くすることができるガスクロスリーク検知方法を提供することができる。この結果、燃料電池を安全に一般の用途(定置用、車載等)に適用することが容易になるという効果がある。   According to the gas cross leak detection method of the present invention, the open circuit voltage difference ΔV is periodically measured during continuous operation of the fuel cell, and when ΔV ≧ 0 (V), a signal indicating the detection of the gas cross leak is generated. By sending it to a desired monitor device (not shown) or the like, it is possible to detect and prevent a sudden drop in the output of a single cell due to a gas cross leak. Therefore, the gas cross leak can be detected with high accuracy without damaging the solid polymer electrolyte membrane, such as increasing the through-hole diameter of the solid polymer electrolyte membrane or generating a large through-hole in the thinned portion. It is possible to provide a gas cross leak detection method capable of extending the time during which the fuel cell can be continuously operated. As a result, there is an effect that it becomes easy to safely apply the fuel cell to general purposes (for stationary use, on-vehicle use, etc.).

以下、まず本発明のガスクロスリーク検知方法について説明し、次に各実施例について図面を参照して詳細に説明する。従来技術の説明で用いた図４に示される固体高分子形燃料電池の単セル２０の電極構造（断面図）および図５に示される燃料電池スタック１２へのガス供給方法は、本発明のガスクロスリーク検知方法の説明においても適宜参照する。   Hereinafter, the gas cross leak detection method of the present invention will be described first, and then each embodiment will be described in detail with reference to the drawings. The electrode structure (cross-sectional view) of the unit cell 20 of the polymer electrolyte fuel cell shown in FIG. 4 and the gas supply method to the fuel cell stack 12 shown in FIG. Reference will also be made as appropriate in the description of the leak detection method.

図１（Ａ）および（Ｂ）は、単セル２０の湿潤状態と貫通孔１３によるガスクロスリーク７の量との関係を示す。図１（Ａ）および（Ｂ）に示されるように、固体高分子電解質膜４には貫通孔１３（径ｄ）が生じており、その貫通孔１３を水１４が塞いでいる。図１（Ａ）は低湿潤状態であって水１４の量は少なく、水１４により塞がれた部分を除く貫通孔１３の径ｄａは大きくて、ガスクロスリーク７の量が多い状態を示す。一方、図１（Ｂ）は高湿潤状態であって水１４の量は図１（Ａ）に示される低湿潤状態の場合よりも多く、水１４により塞がれた部分を除く貫通孔１３の径ｄｂは低湿潤状態の場合の径ｄａより小さくて、ガスクロスリーク７の量は低湿潤状態の場合よりも少ない状態を示す。図１（Ａ）および（Ｂ）に示されるように、固体高分子電解質膜４に貫通孔１３が生じた場合、高湿潤状態（図１（Ｂ））では低湿潤状態（図１（Ａ））よりも、貫通孔１３を水１４が塞ぐ割合は高くなる。すなわち、（ｄ−ｄｂ）／ｄ＞（ｄ−ｄａ）／ｄとなる。従って、高湿潤状態の方が低湿潤状態の方より燃料極２１から空気極２２へ移動する水素の量が少なくなる。この結果、空気極２２で空気２６中の酸素と直接燃焼する水素の量が減るため、開回路電圧の低下も小さくなる。一方、低湿潤状態（図１（Ａ））では、貫通孔１３を塞ぐための水１４が十分に固体高分子電解質膜４中に存在しないため、ガスクロスリーク７の量は高湿潤状態の場合より多くなる。この結果、空気極２２で空気２６中の酸素と直接燃焼する水素の量が増えるため、開回路電圧の低下が大きくなる。従って、開回路電圧状態において、所定の加湿露点の状態（高湿潤状態）から加湿露点を下げた状態（低湿潤状態）の時の開回路電圧の変化量を測定することにより、ガスクロスリーク７の量を検知することができる。すなわち本発明のガスクロスリーク検知方法によれば、単セル２０を構成した固体高分子形燃料電池において、空気極２２または燃料極２１に供給する反応ガス（燃料ガス２５または空気２６）中の加湿量を変えた時に変化する開回路電圧差を測定することにより、固体高分子電解質膜４間のガスクロスリーク７を検知することができる。   1A and 1B show the relationship between the wet state of the single cell 20 and the amount of gas cross leak 7 due to the through-hole 13. As shown in FIGS. 1A and 1B, a through hole 13 (diameter d) is formed in the solid polymer electrolyte membrane 4, and the through hole 13 is blocked by water 14. FIG. 1A shows a state in which the amount of water 14 is small, the diameter da of the through hole 13 excluding the portion blocked by the water 14 is large, and the amount of gas cross leak 7 is large. On the other hand, FIG. 1B shows a high wet state and the amount of water 14 is larger than that in the low wet state shown in FIG. The diameter db is smaller than the diameter da in the low wet state, and the amount of the gas cross leak 7 is smaller than that in the low wet state. As shown in FIGS. 1A and 1B, when the through-hole 13 is formed in the solid polymer electrolyte membrane 4, the wet state (FIG. 1B) is low in the high wet state (FIG. 1B). ), The ratio of the water 14 blocking the through holes 13 is higher. That is, (d−db) / d> (d−da) / d. Therefore, the amount of hydrogen moving from the fuel electrode 21 to the air electrode 22 is smaller in the high wet state than in the low wet state. As a result, since the amount of hydrogen directly combusted with oxygen in the air 26 at the air electrode 22 is reduced, the decrease in open circuit voltage is also reduced. On the other hand, in the low wet state (FIG. 1A), the water 14 for closing the through-holes 13 is not sufficiently present in the solid polymer electrolyte membrane 4, so that the amount of gas cross leak 7 is higher than that in the high wet state. Become more. As a result, the amount of hydrogen directly combusted with oxygen in the air 26 at the air electrode 22 increases, so that the open circuit voltage decreases greatly. Therefore, by measuring the amount of change in the open circuit voltage when the humidified dew point is lowered (low wet state) from the predetermined humidified dew point state (high wet state) in the open circuit voltage state, the gas cross leak 7 The amount can be detected. That is, according to the gas cross leak detection method of the present invention, in the polymer electrolyte fuel cell constituting the single cell 20, the humidification amount in the reaction gas (fuel gas 25 or air 26) supplied to the air electrode 22 or the fuel electrode 21. By measuring the open circuit voltage difference that changes when the value is changed, the gas cross leak 7 between the solid polymer electrolyte membranes 4 can be detected.

本発明のガスクロスリーク検知方法に関し、以下のような測定を行なった。空気極２２の加湿露点温度をＴｄｃ(℃)、その時の開回路電圧をＶＴｄｃ(Ｖ)とし、空気極２２の加湿露点をＴｄｃ(℃)から３０℃下げた時の加湿露点をＴｄｃ_３０(℃)、その時の開回路電圧をＶＴｄｃ_３０(Ｖ)とした場合における、開回路電圧差ΔＶ（Ｖ）＝ＶＴｄｃ−ＶＴｄｃ_３０を測定した。以上の測定後、単セル２０毎に、燃料極２１側に加圧Ｈｅガスにより差圧(０．０５ＭＰａ)をかけてガス透過量を測定した。ガス拡散性が高いＨｅガスを測定ガスに使うことにより、ガスクロスリーク７を感度良く測定することができるためである。なお、電極面積は１００ｃｍ２であった。 Regarding the gas cross leak detection method of the present invention, the following measurements were performed. The humidifying dew point of the air electrode 22 is Tdc (° C), the open circuit voltage at that time is VTdc (V), and the humidifying dew point when the humidifying dew point of the air electrode 22 is lowered by 30 ° C from Tdc (° C) is Tdc_30 (° C). The open circuit voltage difference ΔV (V) = VTdc−VTdc_30 was measured when the open circuit voltage at that time was VTdc_30 (V). After the above measurement, the gas permeation amount was measured for each unit cell 20 by applying a differential pressure (0.05 MPa) to the fuel electrode 21 side with pressurized He gas. This is because the gas cross leak 7 can be measured with high sensitivity by using He gas having high gas diffusibility as the measurement gas. The electrode area was 100 cm 2 .

図２は、Ｈｅガス透過量と開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_３０)との関係をグラフで示す。図２において、横軸は測定ガスであるＨｅガスのガスクロスリーク量（ｃｃ／ｍｉｎ ＠Ｈｅ０．０５ＭＰａ）、縦軸は開回路電圧差ΔＶ(Ｖ)であり、測定点は黒丸印●で示す。図２に示されるように、Ｈｅガスのガスクロスリーク量が多い程、開回路電圧差ΔＶが増加する傾向にある。ここで、開回路電圧差ΔＶが増加するということは、加湿露点をＴｄｃ(℃)から３０℃下げてＴｄｃ_３０(℃)とした時に、開回路電圧が下がったことを意味する。更に、Ｈｅガスのガスクロスリーク量も増加したことから、開回路電圧差ΔＶが変化（増加）した場合には、単セル２０の燃料極２１と空気極２２との間のガスクロスリーク量も変化（増加）したと言うことができる。図２からわかるように、安定した出力を得るためには、つまり開回路電圧差ΔＶを増加させないためには、Ｈｅガスのガスクロスリーク量は１０ｃｃ／ｍｉｎ以下に抑えることが望ましい。言い換えれば、図２の測定結果から、開回路電圧差ΔＶ＜０(Ｖ)であれば、Ｈｅガスのガスクロスリーク量は１０ｃｃ／ｍｉｎ以下に抑えられるため、安定した出力を得ることができる。   FIG. 2 is a graph showing the relationship between the He gas permeation amount and the open circuit voltage difference ΔV (= VTdc−VTdc_30). In FIG. 2, the horizontal axis represents the gas cross leak amount (cc / min @He 0.05 MPa) of He gas as the measurement gas, the vertical axis represents the open circuit voltage difference ΔV (V), and the measurement points are indicated by black circles ●. As shown in FIG. 2, the open circuit voltage difference ΔV tends to increase as the amount of He gas cross leak increases. Here, the increase in the open circuit voltage difference ΔV means that the open circuit voltage has decreased when the humidifying dew point is lowered by 30 ° C. from Tdc (° C.) to Tdc_30 (° C.). Further, since the gas cross leak amount of He gas has increased, when the open circuit voltage difference ΔV changes (increases), the gas cross leak amount between the fuel electrode 21 and the air electrode 22 of the single cell 20 also changes ( Can be said to have increased). As can be seen from FIG. 2, in order to obtain a stable output, that is, in order not to increase the open circuit voltage difference ΔV, it is desirable to suppress the gas cross leak amount of He gas to 10 cc / min or less. In other words, from the measurement result of FIG. 2, if the open circuit voltage difference ΔV <0 (V), the gas cross leak amount of He gas can be suppressed to 10 cc / min or less, and a stable output can be obtained.

以上より、本発明の実施例１によれば、燃料電池の連続運転中に、定期的に開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_３０)を測定し、開回路電圧差ΔＶ≧０(Ｖ)になった時に、ガスクロスリーク７の検知を示す信号を所望のモニタ装置等（不図示）へ送ることにより、ガスクロスリーク７による単セル２０の出力の急低下を未然に検知し防ぐことができる。従って、固体高分子電解質膜４の貫通孔径を増加させたり、薄膜化部１に大きな貫通孔を生じさせる等のように固体高分子電解質膜４を損傷することなくガスクロスリーク７を精度高く検知することができ、燃料電池の連続運転可能な時間を長くすることができるガスクロスリーク検知方法を提供することができる。この結果、燃料電池を安全に一般の用途(定置用、車載等)に適用することが容易になる。   As described above, according to Example 1 of the present invention, the open circuit voltage difference ΔV (= VTdc−VTdc_30) is periodically measured during continuous operation of the fuel cell, and the open circuit voltage difference ΔV ≧ 0 (V) is satisfied. At this time, by sending a signal indicating detection of the gas cross leak 7 to a desired monitor device (not shown) or the like, it is possible to detect and prevent a sudden drop in the output of the single cell 20 due to the gas cross leak 7. Therefore, the gas cross leak 7 is detected with high accuracy without damaging the solid polymer electrolyte membrane 4 such as increasing the through-hole diameter of the solid polymer electrolyte membrane 4 or generating a large through-hole in the thinned portion 1. Therefore, it is possible to provide a gas cross leak detection method capable of extending the time during which the fuel cell can be continuously operated. As a result, it becomes easy to safely apply the fuel cell to general purposes (for stationary use, on-vehicle use, etc.).

実施例１では、開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_３０)の場合について測定した。実施例２では、空気極２２の加湿露点をＴｄｃ(℃)から２０℃下げた時の加湿露点をＴｄｃ_２０(℃)、その時の開回路電圧をＶＴｄｃ_２０(Ｖ)とした場合における、開回路電圧差ΔＶ＝ＶＴｄｃ−ＶＴｄｃ_２０を測定した。実施例２においても実施例１と同様に、以上の測定後、単セル２０毎に、燃料極２１側に加圧Ｈｅガスにより差圧(０．０５ＭＰａ)をかけてガス透過量を測定した。実施例１と同様に、電極面積は１００ｃｍ２であった。 In Example 1, it measured about the case of open circuit voltage difference (DELTA) V (= VTdc-VTdc_30). In Example 2, when the humidifying dew point of the air electrode 22 is lowered by 20 ° C. from Tdc (° C.), the humidifying dew point is Tdc — 20 (° C.), and the open circuit voltage at that time is VTdc — 20 (V). ΔV = VTdc−VTdc — 20 was measured. In Example 2, as in Example 1, after the above measurement, the gas permeation amount was measured for each unit cell 20 by applying a differential pressure (0.05 MPa) to the fuel electrode 21 side with pressurized He gas. Similar to Example 1, the electrode area was 100 cm 2 .

図３は、Ｈｅガス透過量と開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_２０)との関係をグラフで示す。図３において、図２と同様に横軸は測定ガスであるＨｅガスのガスクロスリーク量（ｃｃ／ｍｉｎ ＠Ｈｅ０．０５ＭＰａ）、縦軸は開回路電圧差ΔＶ(Ｖ)であり、測定点は黒三角印▲で示す。図３からわかるように、空気極２２の加湿露点をＴｄｃ(℃) から２０℃下げた時(Ｔｄｃ_２０(℃))も同様に、開回路電圧差ΔＶ＜０(Ｖ)であれば、Ｈｅガスのガスクロスリーク量は１０ｃｃ／ｍｉｎ以下に抑えられるため、安定した出力を得ることができる。   FIG. 3 is a graph showing the relationship between the He gas permeation amount and the open circuit voltage difference ΔV (= VTdc−VTdc — 20). In FIG. 3, the horizontal axis is the gas cross leak amount (cc / min @He 0.05 MPa) of He gas as the measurement gas, the vertical axis is the open circuit voltage difference ΔV (V), and the measurement point is black as in FIG. Indicated by triangle mark ▲. As can be seen from FIG. 3, when the humidification dew point of the air electrode 22 is lowered by 20 ° C. from Tdc (° C.) (Tdc — 20 (° C.)), if the open circuit voltage difference ΔV <0 (V), then the He gas Since the gas cross leak amount is suppressed to 10 cc / min or less, a stable output can be obtained.

実施例１では空気極２２の加湿露点をＴｄｃ(℃)から３０℃下げた場合について開回路電圧差ΔＶを測定し、実施例２ではＴｄｃ(℃)から２０℃下げた場合について開回路電圧差ΔＶ測定した。実際の運転では、Ｔｄｃ(℃)を１０℃以上下げることにより、開回路電圧の検知によってガスクロスリーク７を検知することが可能である。   In Example 1, the open circuit voltage difference ΔV is measured when the humidification dew point of the air electrode 22 is lowered by 30 ° C. from Tdc (° C.), and in Example 2, the open circuit voltage difference is lowered by 20 ° C. from Tdc (° C.). ΔV was measured. In actual operation, the gas cross leak 7 can be detected by detecting the open circuit voltage by lowering Tdc (° C.) by 10 ° C. or more.

以上より、本発明の実施例２によれば、燃料電池の連続運転中に、定期的に（所定の期間毎に）開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_２０)を測定し、開回路電圧差ΔＶ≧０(Ｖ)になった時に、ガスクロスリーク７の検知を示す信号を所望のモニタ装置等（不図示）へ送ることにより、ガスクロスリーク７による単セル２０の出力の急低下を未然に検知し防ぐことができる。実施例１のように空気極２２の加湿露点Ｔｄｃ(℃)を３０℃下げなくても１０℃以上下げることにより、実施例１と同様に、開回路電圧の検知によってガスクロスリーク７を検知することが可能であるという効果を得ることができる。   As described above, according to the second embodiment of the present invention, the open circuit voltage difference ΔV (= VTdc−VTdc — 20) is measured periodically (every predetermined period) during the continuous operation of the fuel cell, and the open circuit voltage difference is measured. When ΔV ≧ 0 (V), a signal indicating the detection of the gas cross leak 7 is sent to a desired monitor device or the like (not shown) to detect a sudden drop in the output of the single cell 20 due to the gas cross leak 7 in advance. Can be prevented. As in the first embodiment, the gas cross leak 7 is detected by detecting the open circuit voltage, as in the first embodiment, by reducing the humidification dew point Tdc (° C.) of the air electrode 22 by 10 ° C. or more without lowering by 30 ° C. Can be obtained.

実施例１および２では、空気極２２の加湿露点Ｔｄｃ(℃)を変えた場合について説明した。しかし、燃料極２１の加湿露点を下げた場合についても同様にしてガスクロスリーク７を検知することが可能であり、空気極２２と燃料極２１との両方の加湿露点を下げた場合についても同様にしてガスクロスリーク７を検知することが可能である。   In Examples 1 and 2, the case where the humidifying dew point Tdc (° C.) of the air electrode 22 is changed has been described. However, the gas cross leak 7 can be detected in the same manner even when the humidification dew point of the fuel electrode 21 is lowered, and similarly when the humidification dew point of both the air electrode 22 and the fuel electrode 21 is lowered. Thus, the gas cross leak 7 can be detected.

本発明の活用例として、一般の用途（定置用または車載用等）における固体高分子型燃料電池（ＰＥＦＣ）による燃料電池発電装置への適用が挙げられる。   As an application example of the present invention, application to a fuel cell power generator using a polymer electrolyte fuel cell (PEFC) in general applications (stationary or in-vehicle use) can be mentioned.

単セル２０の湿潤状態と貫通孔１３によるガスクロスリーク７の量との関係を示す図である。It is a figure which shows the relationship between the wet state of the single cell 20, and the quantity of the gas cross leak 7 by the through-hole 13. FIG. 単セル２０の湿潤状態と貫通孔１３によるガスクロスリーク７の量との関係を示す図である。It is a figure which shows the relationship between the wet state of the single cell 20, and the quantity of the gas cross leak 7 by the through-hole 13. FIG. Ｈｅガス透過量と開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_３０)との関係を示すグラフである。It is a graph which shows the relationship between He gas permeation amount and open circuit voltage difference (DELTA) V (= VTdc-VTdc_30). Ｈｅガス透過量と開回路電圧差ΔＶ(＝ＶＴｄｃ−ＶＴｄｃ_２０)との関係を示すグラフである。It is a graph which shows the relationship between He gas permeation | transmission amount and open circuit voltage difference (DELTA) V (= VTdc-VTdc_20). 固体高分子形燃料電池の最小単位である単電池（単セル）３０の電極構造（断面図）を示す図である。It is a figure which shows the electrode structure (sectional drawing) of the single battery (single cell) 30 which is the minimum unit of a polymer electrolyte fuel cell. 従来の固体高分子形燃料電池の単セル２０を積層した燃料電池スタック１２へのガス供給方法を説明するための図である。It is a figure for demonstrating the gas supply method to the fuel cell stack 12 which laminated | stacked the single cell 20 of the conventional polymer electrolyte fuel cell.

符号の説明Explanation of symbols

１ 電解質膜亀裂部または薄膜部、 ２ａ 燃料極拡散層、 ２ｂ 空気極拡散層、 ３ａ 燃料極触媒層、 ３ｂ 空気極触媒層、 ４ 固体高分子電解質膜、 ５ａ、５ｂ セパレータ、 ６ ガスシール部、 ７ ガスクロスリーク、 ８ａ、８ｂ ガス流通部、 ９、９’ 電圧計、 １０ 燃料極加湿器または改質器、 １１ 空気極加湿器、 １２ 燃料電池スタック、 １３ 貫通孔、 １４ 水、 ２５ 燃料ガス、 ２６ 空気。
DESCRIPTION OF SYMBOLS 1 Electrolytic membrane crack part or thin film part, 2a Fuel electrode diffusion layer, 2b Air electrode diffusion layer, 3a Fuel electrode catalyst layer, 3b Air electrode catalyst layer, 4 Solid polymer electrolyte membrane, 5a, 5b Separator, 6 Gas seal part, 7 Gas cross leak, 8a, 8b Gas distribution section, 9, 9 'Voltmeter, 10 Fuel electrode humidifier or reformer, 11 Air electrode humidifier, 12 Fuel cell stack, 13 Through-hole, 14 Water, 25 Fuel gas, 26 Air.

Claims (4)

燃料極と空気極とにより固体高分子電解質膜を挟持した固体高分子形燃料電池の該固体高分子電解質膜間のガスクロスリーク検知方法であって、
燃料極又は／及び空気極に供給する反応ガス中の加湿量を変えた時に測定された開回路電圧差に基づき、前記固体高分子電解質膜間のガスクロスリークを検知することを特徴とするガスクロスリーク検知方法。 A method for detecting a gas cross leak between solid polymer electrolyte membranes of a polymer electrolyte fuel cell in which a polymer electrolyte membrane is sandwiched between a fuel electrode and an air electrode,
A gas cross leak that detects a gas cross leak between the solid polymer electrolyte membranes based on an open circuit voltage difference measured when a humidification amount in a reaction gas supplied to a fuel electrode and / or an air electrode is changed. Detection method. 請求項１記載のガスクロスリーク検知方法において、前記開回路電圧差の測定は、燃料極又は／及び空気極の加湿露点温度をＴｄｃ(℃)、Ｔｄｃ(℃)の時の開回路電圧をＶＴｄｃ(Ｖ)とし、燃料極又は／及び空気極の加湿露点をＴｄｃ(℃)からＸ℃下げた時の加湿露点をＴｄｃ_Ｘ(℃)、Ｔｄｃ_Ｘ(℃)の時の開回路電圧をＶＴｄｃ_Ｘ(Ｖ)とした場合、前記開回路電圧差としてΔＶ（Ｖ）＝ＶＴｄｃ−ＶＴｄｃ_Ｘを測定することを特徴とするガスクロスリーク検知方法。   2. The gas cross leak detection method according to claim 1, wherein the measurement of the open circuit voltage difference is performed by measuring the open circuit voltage when the humidifying dew point temperature of the fuel electrode and / or the air electrode is Tdc (° C.) and Tdc (° C.) as VTdc ( V), the humidifying dew point when the humidifying dew point of the fuel electrode or / and the air electrode is lowered by X ° C. from Tdc (° C.) is Tdc_X (° C.), and the open circuit voltage at Tdc_X (° C.) is VTdc_X (V) In this case, the gas cross leak detection method is characterized in that ΔV (V) = VTdc−VTdc_X is measured as the open circuit voltage difference. 請求項２記載のガスクロスリーク検知方法において、ガスクロスリークの検知は、前記固体高分子形燃料電池の連続運転中に所定の期間毎に前記開回路電圧差ΔＶ（Ｖ）を測定し、ΔＶ≧０(Ｖ)になった時にガスクロスリークを検知したものとすることを特徴とするガスクロスリーク検知方法。   3. The gas cross leak detection method according to claim 2, wherein the gas cross leak is detected by measuring the open circuit voltage difference ΔV (V) at predetermined intervals during continuous operation of the polymer electrolyte fuel cell, and ΔV ≧ 0. A gas cross leak detection method characterized by detecting a gas cross leak when (V) is reached. 請求項２又は３記載のガスクロスリーク検知方法において、Ｘ℃≧１０℃であることを特徴とするガスクロスリーク検知方法。
4. The gas cross leak detection method according to claim 2, wherein X ° C. ≧ 10 ° C.
JP2004255338A 2004-09-02 2004-09-02 Gas cross leakage detection method Pending JP2006073351A (en)

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