JP2015230782A - Method of inspecting fuel battery film/electrode assembly - Google Patents
Method of inspecting fuel battery film/electrode assembly Download PDFInfo
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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
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Abstract
Description
本発明は、燃料電池用膜・電極接合体の検査方法に関する。 The present invention relates to a method for inspecting a fuel cell membrane / electrode assembly.
燃料電池のアノード及びカソードの電極触媒として、中心粒子及び当該中心粒子を被覆する最外層を備える構造（いわゆるコアシェル構造）を有する触媒微粒子に関する技術が知られている。特許文献１には、パラジウム含有粒子が担持されたカーボン担体を準備する工程、パラジウム含有粒子が担持されたカーボン担体を微細化する工程、及び、前記微細化工程後、前記パラジウム含有粒子に、白金を含む前記最外層を被覆する工程を有することを特徴とする、燃料電池用触媒の製造方法が開示されている。 As an electrode catalyst for an anode and a cathode of a fuel cell, a technology related to catalyst fine particles having a structure (so-called core-shell structure) having a center particle and an outermost layer covering the center particle is known. Patent Document 1 includes a step of preparing a carbon support carrying palladium-containing particles, a step of refining a carbon support carrying palladium-containing particles, and after the refining step, platinum is added to the palladium-containing particles. There is disclosed a method for producing a fuel cell catalyst, comprising the step of coating the outermost layer including:
本発明者が検討した結果、上記特許文献１に開示された燃料電池用触媒は、触媒の状態では高い活性を示すものの、当該触媒を膜・電極接合体に用いた場合に活性が高いか否かは定かではなかった。また、当該触媒を膜・電極接合体に用いた場合の触媒活性を容易に評価する方法も未だ確立してはいない。
本発明は、上記実状を鑑みて成し遂げられたものであり、燃料電池用膜・電極接合体の検査方法を提供することを目的とする。
As a result of the study by the present inventor, the fuel cell catalyst disclosed in Patent Document 1 shows high activity in the catalyst state, but whether the catalyst is used in a membrane / electrode assembly is high. I wasn't sure. In addition, a method for easily evaluating the catalytic activity when the catalyst is used in a membrane / electrode assembly has not yet been established.
The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a method for inspecting a fuel cell membrane / electrode assembly.
本発明の燃料電池用膜・電極接合体の検査方法は、電解質膜の一面側にアノード電極を備え、他面側にカソード電極を備え、かつ当該カソード電極が、パラジウム含有微粒子、及び当該パラジウム含有微粒子の少なくとも一部を被覆する白金含有最外層を備える触媒微粒子を含む燃料電池用膜・電極接合体の検査方法であって、前記膜・電極接合体について電位を掃引することにより得られ、かつ、付与電位を横軸としかつ応答電流値を縦軸とし、さらに応答電流値の内の還元電流値が酸化電流値よりも縦軸の下方向となるように表したサイクリックボルタモグラム曲線において、付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ａとし、付与電位が０．６Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ｂとしたとき、点Ａと点Ｂとの間の前記曲線が、点Ａと点Ｂとを結んだ直線よりも縦軸の上方向に現れる燃料電池用膜・電極接合体を良品と判定し、点Ａと点Ｂとの間の前記曲線が前記直線よりも縦軸の下方向に現れる燃料電池用膜・電極接合体を不良品と判定することを特徴とする。 The method for inspecting a fuel cell membrane / electrode assembly of the present invention comprises an anode electrode on one side of an electrolyte membrane, a cathode electrode on the other side, and the cathode electrode comprising palladium-containing fine particles and the palladium-containing particle. A method for inspecting a membrane / electrode assembly for a fuel cell comprising catalyst fine particles having a platinum-containing outermost layer covering at least a part of the fine particles, obtained by sweeping the potential of the membrane / electrode assembly, and In the cyclic voltammogram curve in which the applied potential is on the horizontal axis, the response current value is on the vertical axis, and the reduction current value of the response current value is below the oxidation current value on the vertical axis. The point corresponding to the reduction current value when the potential is 0.4 V (vs. RHE) is designated as point A, and the point corresponding to the reduction current value when the applied potential is 0.6 V (vs. RHE) is designated as the point. When the above-mentioned curve between point A and point B is determined to be a non-defective fuel cell membrane / electrode assembly that appears above the straight line from the straight line connecting point A and point B, The fuel cell membrane / electrode assembly in which the curve between point A and point B appears below the straight line in the downward direction of the vertical axis is determined as a defective product.
本発明によれば、サイクリックボルタモグラム曲線において前記点Ａ及び点Ｂをそれぞれ特定し、直線ＡＢと、ＡＢ間のサイクリックボルタモグラム曲線との位置関係を調べることにより、燃料電池用膜・電極接合体を評価する方法と同様の正確さで、当該膜・電極接合体に用いられる触媒微粒子の性能をそのまま簡便に評価することができる。 According to the present invention, the point A and the point B are respectively identified in the cyclic voltammogram curve, and the positional relationship between the straight line AB and the cyclic voltammogram curve between AB is examined, whereby the membrane / electrode assembly for a fuel cell is obtained. The performance of the catalyst fine particles used in the membrane-electrode assembly can be simply evaluated as it is with the same accuracy as the method for evaluating the above.
本発明の燃料電池用膜・電極接合体の検査方法は、電解質膜の一面側にアノード電極を備え、他面側にカソード電極を備え、かつ当該カソード電極が、パラジウム含有微粒子、及び当該パラジウム含有微粒子の少なくとも一部を被覆する白金含有最外層を備える触媒微粒子を含む燃料電池用膜・電極接合体の検査方法であって、前記膜・電極接合体について電位を掃引することにより得られ、かつ、付与電位を横軸としかつ応答電流値を縦軸とし、さらに応答電流値の内の還元電流値が酸化電流値よりも縦軸の下方向となるように表したサイクリックボルタモグラム曲線において、付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ａとし、付与電位が０．６Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ｂとしたとき、点Ａと点Ｂとの間の前記曲線が、点Ａと点Ｂとを結んだ直線よりも縦軸の上方向に現れる燃料電池用膜・電極接合体を良品と判定し、点Ａと点Ｂとの間の前記曲線が前記直線よりも縦軸の下方向に現れる燃料電池用膜・電極接合体を不良品と判定することを特徴とする。 The method for inspecting a fuel cell membrane / electrode assembly of the present invention comprises an anode electrode on one side of an electrolyte membrane, a cathode electrode on the other side, and the cathode electrode comprising palladium-containing fine particles and the palladium-containing particle. A method for inspecting a membrane / electrode assembly for a fuel cell comprising catalyst fine particles having a platinum-containing outermost layer covering at least a part of the fine particles, obtained by sweeping the potential of the membrane / electrode assembly, and In the cyclic voltammogram curve in which the applied potential is on the horizontal axis, the response current value is on the vertical axis, and the reduction current value of the response current value is below the oxidation current value on the vertical axis. The point corresponding to the reduction current value when the potential is 0.4 V (vs. RHE) is designated as point A, and the point corresponding to the reduction current value when the applied potential is 0.6 V (vs. RHE) is designated as the point. When the above-mentioned curve between point A and point B is determined to be a non-defective fuel cell membrane / electrode assembly that appears above the straight line from the straight line connecting point A and point B, The fuel cell membrane / electrode assembly in which the curve between point A and point B appears below the straight line in the downward direction of the vertical axis is determined as a defective product.
本発明に使用される燃料電池用膜・電極接合体（以下、膜・電極接合体と称する場合がある。）は、電解質膜の一面側にアノード電極を備え、他面側にカソード電極を備える。膜・電極接合体に用いられる電解質膜、アノード電極、及びカソード電極は、燃料電池を構成する膜・電極接合体に通常使用されるものをそれぞれ用いることができる。アノード電極及びカソード電極は、それぞれガス拡散層を備えていてもよい。
また、膜・電極接合体のカソード電極は、パラジウム含有微粒子、及び当該パラジウム含有微粒子の少なくとも一部を被覆する白金含有最外層を備える触媒微粒子を含む。当該触媒微粒子は、パラジウム及び白金の他にも、銅、コバルト、ニッケル、タングステン、ルテニウム、金、モリブデン、イリジウム、鉄、ロジウム、亜鉛、スズ、及びニオブからなる群より選ばれる少なくとも１つの金属を含んでいてもよい。
The fuel cell membrane / electrode assembly (hereinafter sometimes referred to as a membrane / electrode assembly) used in the present invention includes an anode electrode on one side of an electrolyte membrane and a cathode electrode on the other side. . As the electrolyte membrane, anode electrode, and cathode electrode used in the membrane / electrode assembly, those usually used for the membrane / electrode assembly constituting the fuel cell can be used. Each of the anode electrode and the cathode electrode may include a gas diffusion layer.
The cathode electrode of the membrane / electrode assembly includes palladium-containing fine particles and catalyst fine particles including a platinum-containing outermost layer that covers at least a part of the palladium-containing fine particles. In addition to palladium and platinum, the catalyst fine particles include at least one metal selected from the group consisting of copper, cobalt, nickel, tungsten, ruthenium, gold, molybdenum, iridium, iron, rhodium, zinc, tin, and niobium. May be included.
触媒微粒子の幾何表面積全体を白金単原子層で覆うときの白金量を化学量論比で１とした場合、上記触媒微粒子の白金含有量の化学量論比は１．０〜３．０であることが好ましく、１．５〜２．５であることがより好ましい。当該化学量論比が１よりも小さいとすると、後述する電気量Ｑが正の方向に大きくなる結果、触媒微粒子が失活するおそれがある。一方、触媒微粒子の白金含有量の化学量論比が３．０よりも大きいとすると、活性を有する最外層の表面積が減少する結果、所望の活性が得られないおそれがある。触媒微粒子の白金含有量の上記化学量論比は１．５〜２．５が好ましい。 When the platinum amount when the entire geometric surface area of the catalyst fine particles is covered with a platinum monoatomic layer is set to 1 in the stoichiometric ratio, the stoichiometric ratio of the platinum content of the catalyst fine particles is 1.0 to 3.0. It is preferable that it is 1.5 to 2.5. If the stoichiometric ratio is smaller than 1, the amount of electricity Q, which will be described later, increases in the positive direction, and as a result, the catalyst fine particles may be deactivated. On the other hand, if the stoichiometric ratio of the platinum content of the catalyst fine particles is greater than 3.0, the surface area of the outermost layer having activity may decrease, and as a result, the desired activity may not be obtained. The stoichiometric ratio of the platinum content of the catalyst fine particles is preferably 1.5 to 2.5.
本発明においては、サイクリックボルタモグラム曲線（以下、ＣＶ曲線と称する場合がある。）によって膜・電極接合体の良否判定を行う。当該ＣＶ曲線は、膜・電極接合体について電位を掃引することにより得られ、かつ、付与電位を横軸としかつ応答電流値を縦軸とし、さらに応答電流値の内の還元電流値が酸化電流値よりも縦軸の下方向となるように表したものである。
ＣＶ曲線を得るためのサイクリックボルタンメトリーの条件の一例を以下に示す。
・測定温度：８０℃
・電位掃引速度：５０ｍＶ／ｓｅｃ
アノード側
・アノードガス：水素ガス
・アノードガス流速：０．５Ｌ／ｍｉｎ
・アノードガス相対湿度：ＲＨ１００％
・アノードガス出口圧：１０１．３ｋＰａ−ａｂｓ．
カソード側
・カソードガス：窒素封入（ガス流速：０Ｌ／ｍｉｎ）
・カソードガス相対湿度：ＲＨ１００％
・カソードガス出口圧：１０１．３ｋＰａ−ａｂｓ．
In the present invention, the quality of the membrane / electrode assembly is determined by a cyclic voltammogram curve (hereinafter sometimes referred to as a CV curve). The CV curve is obtained by sweeping the potential of the membrane / electrode assembly, the applied potential is on the horizontal axis, the response current value is on the vertical axis, and the reduction current value of the response current value is the oxidation current. It is expressed so that the vertical axis is below the value.
An example of cyclic voltammetry conditions for obtaining a CV curve is shown below.
・ Measurement temperature: 80 ℃
-Potential sweep speed: 50 mV / sec
Anode side ・ Anode gas: Hydrogen gas ・ Anode gas flow rate: 0.5 L / min
・ Anode gas relative humidity: RH100%
Anode gas outlet pressure: 101.3 kPa-abs.
Cathode side ・ Cathode gas: filled with nitrogen (gas flow rate: 0 L / min)
・ Cathode gas relative humidity: RH100%
Cathode gas outlet pressure: 101.3 kPa-abs.
膜・電極接合体の評価においては、まず、ＣＶ曲線において、基準となる２点を以下の通り決定する。すなわち、当該ＣＶ曲線において、付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ａとし、付与電位が０．６Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ｂとする。
ここで、付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値とは、膜・電極接合体の通常の運転において、一般に触媒担体カーボンの電気二重層容量を示す電流値である。
また、一般に白金表面における酸素還元電流値は、０．８Ｖ（ｖｓ．ＲＨＥ）付近で最大となるため、０．６Ｖ（ｖｓ．ＲＨＥ）付近では殆ど酸素還元電流は流れないと考えられる。通常、白金表面の場合は０．６Ｖ（ｖｓ．ＲＨＥ）から０．４Ｖ（ｖｓ．ＲＨＥ）に向かって還元電流がさらに減少していくことになるが、仮にこれらの電位の間に副反応が生じた場合には、酸素還元電流とは異なる還元電流に起因するピークが出現することになる。
In the evaluation of the membrane / electrode assembly, first, two reference points in the CV curve are determined as follows. That is, in the CV curve, a point corresponding to a reduction current value when the applied potential is 0.4 V (vs. RHE) is set as a point A, and a reduction current value when the applied potential is 0.6 V (vs. RHE). Let the point corresponding to be point B.
Here, the reduction current value when the applied potential is 0.4 V (vs. RHE) is a current value that generally indicates the electric double layer capacity of the catalyst-supporting carbon in the normal operation of the membrane-electrode assembly.
In general, the oxygen reduction current value on the platinum surface is maximum near 0.8 V (vs. RHE), so that it is considered that almost no oxygen reduction current flows near 0.6 V (vs. RHE). Normally, in the case of the platinum surface, the reduction current further decreases from 0.6 V (vs. RHE) to 0.4 V (vs. RHE), but there is a side reaction between these potentials. When it occurs, a peak due to a reduction current different from the oxygen reduction current appears.
次に、点Ａと点Ｂとを結んだ直線（以下、直線ＡＢと称する場合がある。）と、点Ａと点Ｂとの間の前記曲線（以下、曲線ＡＢと称する場合がある。）との位置関係を調べ、以下の通り良否を判定する。すなわち、曲線ＡＢが直線ＡＢよりも縦軸の上方向に現れる燃料電池用膜・電極接合体については、良品と判定する。一方、曲線ＡＢが直線ＡＢよりも縦軸の下方向に現れる燃料電池用膜・電極接合体については、不良品と判定する。
このように判定できる根拠は以下の通りである。すなわち、後述する図２及び図４から明らかなように、点Ａと点Ｂとを直線で結ぶことにより、直線ＡＢとＣＶ曲線とに挟まれた、所定の面積を有する１又は２以上の図形が得られる。当該各図形の面積は、それぞれ電気量Ｑに相当する。ここで、直線ＡＢを基準として、ＣＶ曲線が直線ＡＢよりも縦軸に沿って上方向に現れている図形（すなわち上に凸の図形）の面積を負の電気量であると換算し、ＣＶ曲線が直線ＡＢよりも縦軸に沿って下方向に現れている図形（すなわち下に凸の図形）の面積を正の電気量であると換算する。１又は２以上の図形に係る電気量の総和が負の場合は、後述する実施例１に示すように電極活性が高くなる結果、良品であると判定できる。曲線ＡＢが直線ＡＢよりも縦軸の上方向に現れる場合は、良品の典型例である。一方、１又は２以上の図形に係る電気量の総和が正の場合は、後述する比較例１に示すように電極活性が低くなる結果、不良品であると判定できる。曲線ＡＢが直線ＡＢよりも縦軸の下方向に現れる場合は、不良品の典型例である。
Next, a straight line connecting point A and point B (hereinafter sometimes referred to as straight line AB) and the curve between point A and point B (hereinafter sometimes referred to as curve AB). And the quality is determined as follows. That is, a fuel cell membrane / electrode assembly in which the curve AB appears above the straight line AB in the vertical axis direction is determined to be a non-defective product. On the other hand, a fuel cell membrane / electrode assembly in which the curve AB appears below the straight line AB in the vertical axis is determined to be defective.
The basis for this determination is as follows. That is, as will be apparent from FIGS. 2 and 4 to be described later, one or more figures having a predetermined area sandwiched between the straight line AB and the CV curve by connecting the point A and the point B with a straight line. Is obtained. The area of each figure corresponds to the amount of electricity Q. Here, using the straight line AB as a reference, the area of the figure in which the CV curve appears upward along the vertical axis with respect to the straight line AB (that is, the figure convex upward) is converted to a negative electric quantity, and the CV The area of the figure in which the curve appears downward along the vertical axis from the straight line AB (that is, the figure convex downward) is converted to a positive quantity of electricity. When the total amount of electricity related to one or two or more figures is negative, it can be determined that the electrode is non-defective as a result of the increased electrode activity as shown in Example 1 described later. The case where the curve AB appears above the straight line AB is a typical example of a good product. On the other hand, when the total amount of electricity related to one or more figures is positive, it can be determined that the product is defective as a result of lower electrode activity as shown in Comparative Example 1 described later. When the curve AB appears below the straight line AB, it is a typical example of a defective product.
以上の通り、本発明においては、ＣＶ曲線において、上記点Ａ及び点Ｂを特定し、直線ＡＢと曲線ＡＢとのいずれが縦軸の上方向に現れるかを調べることにより、燃料電池用膜・電極接合体を評価する方法と同様の正確さで、当該膜・電極接合体に用いられる触媒微粒子の性能をそのまま簡便に評価することができる。 As described above, in the present invention, in the CV curve, the point A and the point B are specified, and by examining which of the straight line AB and the curve AB appears in the upward direction of the vertical axis, With the same accuracy as the method of evaluating the electrode assembly, the performance of the catalyst fine particles used in the membrane / electrode assembly can be simply evaluated as it is.
以下に、実施例及び比較例を挙げて、本発明を更に具体的に説明するが、本発明は、この実施例のみに限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to only these examples.
１．燃料電池電極用インクの製造
［製造例１］
まず、触媒微粒子担持カーボン、アイオノマ（Ｎａｆｉｏｎ（商品名））、及び分散媒を準備した。ここで、触媒微粒子とは、パラジウム微粒子、及び当該パラジウム微粒子の全表面を覆う白金層を備える触媒微粒子である。
次に、以下の条件（１）及び（２）をいずれも満たすように、触媒微粒子担持カーボン、アイオノマ、及び分散媒を混合した。
（１）触媒微粒子担持カーボンにおけるカーボンとアイオノマとの体積比を１：１とする。
（２）触媒微粒子担持カーボン及びアイオノマの合計の質量を、混合物（インク）の総質量の３．０質量％とする。
1. Production of ink for fuel cell electrode [Production Example 1]
First, catalyst fine particle carrying carbon, ionomer (Nafion (trade name)), and a dispersion medium were prepared. Here, the catalyst fine particles are catalyst fine particles including palladium fine particles and a platinum layer covering the entire surface of the palladium fine particles.
Next, the catalyst fine particle-supporting carbon, the ionomer, and the dispersion medium were mixed so as to satisfy both of the following conditions (1) and (2).
(1) The volume ratio of carbon to ionomer in the catalyst fine particle-supporting carbon is 1: 1.
(2) The total mass of the catalyst fine particle-supporting carbon and ionomer is 3.0 mass% of the total mass of the mixture (ink).
最後に、得られた混合物を遊星ビーズミル（Ｒｅｔｓｃｈ製、製品番号：ＰＭ２００）により１５０ｒｐｍ／３ｈｒの条件で混合することにより、分散媒中に触媒微粒子担持カーボン及びアイオノマを高分散させ、製造例１の燃料電池電極用インク（以下、製造例１のインクと称する場合がある。）が得られた。 Finally, the obtained mixture was mixed with a planetary bead mill (manufactured by Retsch, product number: PM200) at 150 rpm / 3 hr to highly disperse the catalyst fine particle-supporting carbon and ionomer in the dispersion medium. An ink for a fuel cell electrode (hereinafter sometimes referred to as ink of Production Example 1) was obtained.
［製造例２］
触媒微粒子として、パラジウム微粒子、及び当該パラジウム微粒子の一部を覆う白金層を備えるものを用いたこと以外は、製造例１と同様にして、製造例２の燃料電池電極用インク（以下、製造例２のインクと称する場合がある。）を調製した。
[Production Example 2]
The fuel cell electrode ink of Production Example 2 (hereinafter, Production Example) was prepared in the same manner as Production Example 1 except that the catalyst fine particles used were palladium fine particles and those having a platinum layer covering a part of the palladium fine particles. 2).
２．膜・電極接合体の製造
［実施例１］
製造例１のインクを、単位面積当たりの電極における白金質量が０．１ｍｇ／ｃｍ２となるように、テフロン（登録商標）基板上にスプレー塗布して乾燥させた。次に、乾燥したインクを電解質膜の一方の面に１５０℃で熱転写し、カソード電極を形成した。一方、市販の白金担持カーボンを含む燃料電池電極用インクを用いて、上記同様に塗布及び乾燥を行った後、電解質膜の他の一方の面に１５０℃で熱転写し、アノード電極を形成することにより、実施例１の膜・電極接合体を作製した。
2. Manufacture of membrane / electrode assembly [Example 1]
The ink of Production Example 1 was spray-coated on a Teflon (registered trademark) substrate and dried so that the platinum mass in the electrode per unit area was 0.1 mg / cm 2 . Next, the dried ink was thermally transferred to one surface of the electrolyte membrane at 150 ° C. to form a cathode electrode. On the other hand, after applying and drying in the same manner as described above using commercially available platinum-supported carbon-containing ink, platinum is thermally transferred to the other surface of the electrolyte membrane at 150 ° C. to form an anode electrode. Thus, the membrane / electrode assembly of Example 1 was produced.
［比較例１］
電解質膜の一方の面に対し製造例２のインクを用い、もう一方の面に対し市販の白金担持カーボンを含む燃料電池電極用インクを用いたこと以外は、実施例１と同様に電極の形成を行い、比較例１の膜・電極接合体を作製した。
[Comparative Example 1]
Formation of electrodes as in Example 1 except that the ink of Production Example 2 was used for one side of the electrolyte membrane and the commercially available ink for fuel cell electrodes containing platinum-supported carbon was used for the other side. The membrane / electrode assembly of Comparative Example 1 was produced.
３．膜・電極接合体のサイクリックボルタンメトリー
実施例１及び比較例１の膜・電極接合体をそれぞれ燃料電池セルに組み込み、以下の条件でサイクリックボルタンメトリーを行った。
・測定温度：８０℃
・電位掃引速度：５０ｍＶ／ｓｅｃ
アノード側
・アノードガス：水素ガス
・アノードガス流速：０．５Ｌ／ｍｉｎ
・アノードガス相対湿度：ＲＨ１００％
・アノードガス出口圧：１０１．３ｋＰａ−ａｂｓ．
カソード側
・カソードガス：窒素封入（ガス流速：０Ｌ／ｍｉｎ）
・カソードガス相対湿度：ＲＨ１００％
・カソードガス出口圧：１０１．３ｋＰａ−ａｂｓ．
3. Cyclic Voltammetry of Membrane / Electrode Assembly Each of the membrane / electrode assemblies of Example 1 and Comparative Example 1 was incorporated into a fuel cell, and cyclic voltammetry was performed under the following conditions.
・ Measurement temperature: 80 ℃
-Potential sweep speed: 50 mV / sec
Anode side ・ Anode gas: Hydrogen gas ・ Anode gas flow rate: 0.5 L / min
・ Anode gas relative humidity: RH100%
Anode gas outlet pressure: 101.3 kPa-abs.
Cathode side ・ Cathode gas: filled with nitrogen (gas flow rate: 0 L / min)
・ Cathode gas relative humidity: RH100%
Cathode gas outlet pressure: 101.3 kPa-abs.
図１は、実施例１及び比較例１の膜・電極接合体のＣＶを重ねて示したグラフである。また、図２は、図１に示した実施例１の膜・電極接合体のＣＶ中、長方形で囲った部分の拡大図である。さらに、図４は、図１に示した比較例１の膜・電極接合体のＣＶ中、長方形で囲った部分の拡大図である。
図４に示すように、比較例１のＣＶにおいては、付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ａとし、付与電位が０．６Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ｂとしている。図４から分かる通り、ＡＢ間のＣＶ曲線は、直線ＡＢよりも電流の縦軸の下方向に現れる。したがって、比較例１の膜・電極接合体は不良品であると判定できる。
一方、図２においても同様に、点Ａ及び点Ｂをそれぞれ特定する。図２から分かる通り、ＡＢ間のＣＶ曲線は、直線ＡＢよりも電流の縦軸の上方向に現れる。したがって、実施例１の膜・電極接合体は良品であると判定できる。
FIG. 1 is a graph in which CVs of the membrane-electrode assemblies of Example 1 and Comparative Example 1 are overlaid. FIG. 2 is an enlarged view of a portion surrounded by a rectangle in the CV of the membrane-electrode assembly of Example 1 shown in FIG. Further, FIG. 4 is an enlarged view of a portion surrounded by a rectangle in the CV of the membrane-electrode assembly of Comparative Example 1 shown in FIG.
As shown in FIG. 4, in the CV of Comparative Example 1, the point corresponding to the reduction current value when the applied potential is 0.4 V (vs. RHE) is point A, and the applied potential is 0.6 V (vs. RHE). A point corresponding to the reduction current value at the time of RHE) is set as a point B. As can be seen from FIG. 4, the CV curve between AB appears below the vertical axis of the current from the straight line AB. Therefore, it can be determined that the membrane / electrode assembly of Comparative Example 1 is a defective product.
On the other hand, also in FIG. 2, the point A and the point B are specified similarly. As can be seen from FIG. 2, the CV curve between AB appears above the vertical axis of the current with respect to the straight line AB. Therefore, it can be determined that the membrane / electrode assembly of Example 1 is a non-defective product.
４．膜・電極接合体の放電試験
実施例１及び比較例１の膜・電極接合体をそれぞれ燃料電池セルに組み込み、以下の条件で放電試験を行った。
・測定温度：８０℃
・電極面積：１３ｃｍ２
アノード側
・アノードガス：水素ガス
・アノードガス流速：１．０Ｌ／ｍｉｎ
・アノードガス相対湿度：ＲＨ１００％
・アノードガス出口圧：１５１．３ｋＰａ−ａｂｓ．
カソード側
・カソードガス：空気
・カソードガス流速：２．０Ｌ／ｍｉｎ
・カソードガス相対湿度：ＲＨ１００％
・カソードガス出口圧：１５１．３ｋＰａ−ａｂｓ．
4). Discharge Test of Membrane / Electrode Assembly The membrane / electrode assemblies of Example 1 and Comparative Example 1 were each incorporated in a fuel cell, and a discharge test was performed under the following conditions.
・ Measurement temperature: 80 ℃
-Electrode area: 13 cm 2
Anode side ・ Anode gas: Hydrogen gas ・ Anode gas flow rate: 1.0 L / min
・ Anode gas relative humidity: RH100%
Anode gas outlet pressure: 151.3 kPa-abs.
Cathode side ・ Cathode gas: Air ・ Cathode gas flow rate: 2.0 L / min
・ Cathode gas relative humidity: RH100%
Cathode gas outlet pressure: 151.3 kPa-abs.
図３は、実施例１及び比較例１の膜・電極接合体のＩ−Ｖ曲線を並べて示したグラフである。図３から明らかなように、電流密度条件の全範囲において、実施例１の膜・電極接合体は、比較例１の膜・電極接合体よりも高い電位を示すことが分かる。以上より、実施例１の膜・電極接合体は、比較例１の膜・電極接合体よりも電極活性が高いことが確認できる。 FIG. 3 is a graph showing IV curves of the membrane / electrode assemblies of Example 1 and Comparative Example 1 side by side. As can be seen from FIG. 3, the membrane / electrode assembly of Example 1 shows a higher potential than the membrane / electrode assembly of Comparative Example 1 over the entire range of current density conditions. From the above, it can be confirmed that the membrane / electrode assembly of Example 1 has higher electrode activity than the membrane / electrode assembly of Comparative Example 1.
５．結論
以上より、本発明に係る検査方法を用いた燃料電池用膜・電極接合体の性能評価と、放電試験による燃料電池用膜・電極接合体の性能評価とが一致した。よって、本発明に係る検査方法は、燃料電池用膜・電極接合体を評価する方法と同様の正確さで、当該膜・電極接合体に用いられる触媒微粒子の性能をそのまま簡便に評価できる方法であることが分かる。
5). Conclusion From the above, the performance evaluation of the membrane / electrode assembly for fuel cells using the inspection method according to the present invention coincided with the performance evaluation of the membrane / electrode assembly for fuel cells by the discharge test. Therefore, the inspection method according to the present invention is a method that can simply and simply evaluate the performance of the catalyst fine particles used in the membrane-electrode assembly with the same accuracy as the method of evaluating the membrane-electrode assembly for fuel cells. I understand that there is.
Claims (1)
前記膜・電極接合体について電位を掃引することにより得られ、かつ、付与電位を横軸としかつ応答電流値を縦軸とし、さらに応答電流値の内の還元電流値が酸化電流値よりも縦軸の下方向となるように表したサイクリックボルタモグラム曲線において、
付与電位が０．４Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ａとし、付与電位が０．６Ｖ（ｖｓ．ＲＨＥ）のときの還元電流値に対応する点を点Ｂとしたとき、点Ａと点Ｂとの間の前記曲線が、点Ａと点Ｂとを結んだ直線よりも縦軸の上方向に現れる燃料電池用膜・電極接合体を良品と判定し、点Ａと点Ｂとの間の前記曲線が前記直線よりも縦軸の下方向に現れる燃料電池用膜・電極接合体を不良品と判定することを特徴とする、燃料電池用膜・電極接合体の検査方法。 Catalyst fine particles comprising an anode electrode on one side of the electrolyte membrane, a cathode electrode on the other side, and the cathode electrode comprising palladium-containing fine particles and a platinum-containing outermost layer covering at least part of the palladium-containing fine particles A method for inspecting a fuel cell membrane / electrode assembly comprising:
The membrane-electrode assembly is obtained by sweeping the potential, the applied potential is on the horizontal axis, the response current value is on the vertical axis, and the reduction current value of the response current value is higher than the oxidation current value. In the cyclic voltammogram curve expressed so that it is below the axis,
A point corresponding to the reduction current value when the applied potential is 0.4 V (vs. RHE) is a point A, and a point corresponding to the reduction current value when the applied potential is 0.6 V (vs. RHE) is a point B. When the above-mentioned curve between point A and point B is determined to be a non-defective fuel cell membrane / electrode assembly that appears above the straight line from the straight line connecting point A and point B, A fuel cell membrane / electrode assembly, wherein the fuel cell membrane / electrode assembly in which the curve between point A and point B appears in the downward direction of the vertical axis from the straight line is determined as a defective product. Body inspection method.
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