JP2006059745A - Apparatus for monitoring cell voltage of hydrogen fuel cell, and method for using the same - Google Patents
Apparatus for monitoring cell voltage of hydrogen fuel cell, and method for using the same Download PDFInfo
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Abstract
Description
本発明は、水素燃料電池のセル電圧をモニターすることで、水素燃料の性状を簡単に分析可能で、しかも実用的な安価に提供することができる水素燃料電池のセル電圧モニター装置及びその利用方法に関する。 The present invention relates to a cell voltage monitoring device for a hydrogen fuel cell and a method for using the same, which can easily analyze the properties of the hydrogen fuel by monitoring the cell voltage of the hydrogen fuel cell and can be provided at a practical and low cost. About.
現在、世界的に水素燃料電池自動車の普及が推進されている。この水素燃料電池自動車に使用される燃料電池は不純物の影響を受けやすい為、燃料となる水素については高純度のものが必要とされるものであり、かかる点から国際的に統一された性状規格の設定が進められている。このような状況下にあって規格が設定されたとしても実際の使用時において性状規格に適合しているかを保証する為には、可能な限り水素燃料電池自動車に充填する直前、すなわち水素ディスペンサーの個所において分析することが望ましい。 Currently, the spread of hydrogen fuel cell vehicles is being promoted worldwide. Since the fuel cell used in this hydrogen fuel cell vehicle is easily affected by impurities, high purity hydrogen is required for the fuel hydrogen. The setting of is advanced. Even in such a situation, even if the standard is set, in order to guarantee that it meets the property standard in actual use, as much as possible immediately before filling the hydrogen fuel cell vehicle, that is, the hydrogen dispenser It is desirable to analyze in place.
しかしながら、水素に含まれる不純物を正確に分析するには、現状では購入額が少なくとも数千万円レベルの種々の分析装置を必要とする。また、分析装置の中には正確な分析を行うために試料のサンプリングと分析に熟練を要するものがあり、コスト的・人員的な観点から水素ステーション毎に分析装置を装備し、分析者を配置することは現実的ではない。対応策として、分析作業の外注が挙げられるが、現状においては分析費用が年間数百万円（分析頻度を数ヶ月毎とした場合）となり、人員面は解決できてもコスト的にはまだ高額の域を出ない。 However, in order to accurately analyze impurities contained in hydrogen, at present, various analyzers with a purchase amount of at least tens of millions of yen are required. Some analyzers require skill in sampling and analysis of samples in order to carry out accurate analysis. From the viewpoint of cost and personnel, each hydrogen station is equipped with an analyzer and an analyst is assigned. To do is not realistic. As a countermeasure, outsourcing of analysis work can be mentioned, but currently the analysis cost is several million yen per year (when the analysis frequency is set to every few months), and even though the personnel can be solved, the cost is still high. The area of
ところで、水素燃料性状を管理するための従来の典型的な先行技術の例としてはＰＥＭ燃料電池に対するＣＯ濃度を監視する発明に関するものがある。（例えば、特許文献１、２参照。）。この特許文献１、２は、何れもＣＯセンサー及び改質燃料蒸気のＣＯ濃度を制御するＰＥＭ燃料電池へのＣＯ濃度を監視する方法に関するもので、小型のＰＥＭ燃料電池をプローブとして用いている敏感なＣＯセンサーと、燃料電池システムの作動を制御するための手段としてＰＥＭ燃料電池への改質物供給の流れにおけるＣＯ濃度をリアルタイムで監視するための方法についての発明である。 By the way, as an example of a conventional prior art for managing hydrogen fuel properties, there is an invention relating to an invention for monitoring the CO concentration for a PEM fuel cell. (For example, refer to Patent Documents 1 and 2.) Patent Documents 1 and 2 both relate to a CO sensor and a method for monitoring the CO concentration in a PEM fuel cell that controls the CO concentration of reformed fuel vapor, and are sensitive to using a small PEM fuel cell as a probe. And a method for monitoring in real time the CO concentration in the reformate supply flow to the PEM fuel cell as a means to control the operation of the fuel cell system.
水素燃料を消費する各種装置の中で例えば水素燃料電池自動車について見た場合、高純度が要求される水素燃料が不純物の影響で純度が下がってくると水素燃料電池自動車（燃料電池自体）の耐久性低下に直接つながるために、高純度保持が強く望まれるが、燃料電池の耐久性の低下度合いはＣＯだけでなく、他の含有成分である硫黄、蟻酸、ホルムアルデヒド等の濃度によっても影響を受けるものである。 When looking at hydrogen fuel cell vehicles, for example, among various devices that consume hydrogen fuel, the durability of hydrogen fuel cell vehicles (the fuel cell itself) is reduced when the purity of hydrogen fuel that requires high purity decreases due to impurities. High purity retention is strongly desired because it directly leads to a decrease in performance, but the degree of decrease in durability of the fuel cell is affected not only by CO but also by the concentration of other components such as sulfur, formic acid, formaldehyde, etc. Is.
上述する特許文献１、２の発明では、ＣＯ濃度を監視することによって高純度化のための諸対策を講じることができるが、ＣＯ以外の硫黄など他の成分の影響については何等対応できないために高純度保持対策面で万全とは言い難い問題を有している。
水素燃料における水素性状を合理的にかつ経済的に十分管理することは水素燃料電池を安定して稼動させる為に不可欠な事項である。しかしながら、分析装置は数千万円レベルであり、分析作業自体も熟練を要する等、必要なときに簡単に水素性状を分析することは現状容易ではない。また、上記のようにＣＯ以外にも水素燃料電池の耐久性に影響を及ぼす不純物が存在する為、特許文献で示す監視方法では水素燃料性状分析として不十分である。そこで、正確で簡単かつ安価な水素性状を分析できる機器が望まれている。 It is indispensable to reasonably and economically manage the hydrogen properties of hydrogen fuel in order to stably operate the hydrogen fuel cell. However, it is not easy at present to easily analyze the hydrogen properties when necessary, for example, the analysis apparatus is in the tens of millions of yen level and the analysis work itself requires skill. In addition, as described above, impurities other than CO that affect the durability of the hydrogen fuel cell exist, and therefore, the monitoring method disclosed in the patent document is insufficient as a hydrogen fuel property analysis. Therefore, there is a demand for an apparatus that can analyze hydrogen properties accurately, simply and inexpensively.
かかる課題を解決するべく、ここに本発明は案出されるに至ったものであって、従って、請求項１に記載された発明は、高純度水素を供給する水素供給ライン（Ｌ1）に連通する水素モニターライン（Ｌ2）に接続されるモニター用水素燃料電池（４）と、上記モニター用水素燃料電池（４）による未利用水素を上記水素モニターライン（Ｌ2）に環流させる循環ライン（Ｌ3）と、不純物を含有する未利用水素をパージさせるために上記循環ライン（Ｌ3）に付設されるパージライン（Ｌ4）と、清浄空気をモニター用水素燃料電池（４）に給送するための送気ライン（Ｌ5）と、モニター用水素燃料電池（４）が前記高純度水素と前記清浄空気の供給により発電した電力を定電流で消費させる定電流負荷回路（１１）と、積算発電時間(T)及びセル電圧（Ｖ）を測定するために定電流負荷回路（１１）に付設される積算発電時間計測手段（１２）及びセル電圧測定手段（１３）と、積算発電時間(T)に対するセル電圧（Ｖ）の許容上限値（Ｖｎ）及び許容下限値（Ｖa）を記憶する判別基準データ記憶手段（１４ｂ）と、を備えて成り、上記積算発電時間(T)に対するセル電圧（Ｖ）の許容上限値（Ｖｎ）及び許容下限値（Ｖa）は、純水素及び水素燃料規格値下限の水素の2種を用いての前記定電流負荷回路（１１）による負荷テストを行わせて得られる、発電時間とセル電圧の関係になる２種のセル電圧経時変化により規定されることを特徴とするセル電圧モニター装置である。 In order to solve this problem, the present invention has been devised here. Therefore, the invention described in claim 1 communicates with a hydrogen supply line (L1) for supplying high-purity hydrogen. A monitoring hydrogen fuel cell (4) connected to the hydrogen monitoring line (L2), and a circulation line (L3) for circulating unused hydrogen from the monitoring hydrogen fuel cell (4) to the hydrogen monitoring line (L2); A purge line (L4) attached to the circulation line (L3) for purging unused hydrogen containing impurities, and an air supply line for supplying clean air to the monitor hydrogen fuel cell (4) (L5), a constant current load circuit (11) for consuming the power generated by the monitoring hydrogen fuel cell (4) by supplying the high-purity hydrogen and the clean air at a constant current, an integrated power generation time (T) and Cell power Integrated power generation time measuring means (12) and cell voltage measuring means (13) attached to the constant current load circuit (11) for measuring the pressure (V), and the cell voltage (V) with respect to the integrated power generation time (T) Discriminating reference data storage means (14b) for storing the allowable upper limit value (Vn) and the allowable lower limit value (Va), and the allowable upper limit value of the cell voltage (V) with respect to the integrated power generation time (T) ( Vn) and the allowable lower limit (Va) are obtained by performing a load test by the constant current load circuit (11) using two kinds of hydrogen, pure hydrogen and hydrogen at the lower limit of the hydrogen fuel standard value. The cell voltage monitoring device is characterized in that it is defined by two types of cell voltage changes with time in relation to voltage.
また、本発明の請求項２に係る発明は、請求項1に記載のセル電圧モニター装置を用いて測定した任意の積算発電時間（Ｔｉ）に対するセル電圧（Ｖｉ）が許容上限値（Ｖｎ）と許容下限値（Ｖa）の範囲内にあるか否かを判断することに基づき高純度水素の燃料性状の正常・異常を判別することを特徴とする水素燃料性状の判別方法である。 Further, in the invention according to claim 2 of the present invention, the cell voltage (Vi) with respect to an arbitrary accumulated power generation time (Ti) measured using the cell voltage monitor device according to claim 1 is an allowable upper limit value (Vn). A hydrogen fuel property determination method characterized by determining normality / abnormality of fuel property of high-purity hydrogen based on determining whether the value is within the allowable lower limit (Va).
また、本発明の請求項３に係る発明は、請求項2記載の水素燃料性状の判別方法において、上記燃料性状が正常の場合に、積算発電時間（Ｔｉ）に対するセル電圧（Ｖｉ）の変化率を算定し、その変化率が前記許容下限値（Ｖa）における変化率を下回ることに基づき高純度水素の燃料性状の悪化を予測することを特徴とする水素燃料性状の判別方法である。 The invention according to claim 3 of the present invention is the hydrogen fuel property determination method according to claim 2, wherein the rate of change of the cell voltage (Vi) with respect to the integrated power generation time (Ti) when the fuel property is normal. And the deterioration of the fuel property of high-purity hydrogen is predicted based on the fact that the rate of change falls below the rate of change at the allowable lower limit (Va).
更にまた、本発明の請求項４に係る発明は、請求項3に記載の水素燃料性状の判別方法において、上記燃料性状の悪化を予測することに基づき、高純度水素中に供給する酸素濃度を調節して、モニター用水素燃料電池（４）のセル電圧の回復を図ることを特徴とする水素燃料性状の判別方法である。 Furthermore, the invention according to claim 4 of the present invention is the method for determining the hydrogen fuel property according to claim 3, wherein the oxygen concentration supplied to the high purity hydrogen is determined based on the prediction of the deterioration of the fuel property. This is a method for determining the hydrogen fuel property, characterized by adjusting and recovering the cell voltage of the monitor hydrogen fuel cell (4).
更にまた、本発明の請求項５に係る発明は、請求項1に記載のセル電圧モニター装置を用いて測定したモニター用水素燃料電池（４）の積算発電時間（Ｔｉ）におけるセル電圧（Ｖｉ）が許容上限値（Ｖｎ）と許容下限値（Ｖa）の範囲内にあるか否かと、積算発電時間（Ｔｉ）におけるセル電圧（Ｖｉ）の変化率が許容下限値（Ｖa）における変化率よりも大きいか小さいかを合わせて判断することを特徴とする水素燃料電池（４）の性能検査方法である。 Furthermore, the invention according to claim 5 of the present invention is the cell voltage (Vi) in the accumulated power generation time (Ti) of the monitoring hydrogen fuel cell (4) measured using the cell voltage monitoring device according to claim 1. Is within the range between the allowable upper limit value (Vn) and the allowable lower limit value (Va), and the rate of change of the cell voltage (Vi) in the integrated power generation time (Ti) is greater than the rate of change in the allowable lower limit value (Va). It is a performance inspection method of a hydrogen fuel cell (4) characterized by judging whether it is large or small.
請求項１に記載される装置により、請求項２および３にて記載される判別方法を用いることで、特に水素燃料電池をモニターとして使用し、判別基準データとモニター実測から得られる積算発電時間Ｔに対するセル電圧Ｖの測定値又は変化率ΔV／ΔTをリアルタイムで比較するようにしたことで、以下のような効果が期待できる。即ち、
A．常時水素燃料性状をモニターすることから規格から外れた場合に直ちに検知できて即座に対処できる。
B．モニター用水素燃料電池は、ＭＥＡ（Ｍｅｍｂｒａｎｅ
Ｅｌｅｃｔｒｏｄｅ Ａｓｓｅｍｂｌｙ＝膜／電極接合体）を交換すれば、モニター装置全体としては長期間継続使用できる。尚、交換頻度は１年に１回程度でよい。
Ｃ．セル電圧の変化率が異常な値を示した場合、数％程度の酸素を含む水素を導入してセル電圧の変化率が復帰すればCOが原因、復帰しなければ硫黄などの他の成分が原因として、不純物物質の特定も可能である。
Ｄ．判別基準データを適宜変更することで水素性状モニターのみならず、製品として出荷前の仕様の異なる燃料電池の性能を簡単に検査できる装置としても利用できる。
Ｅ．従来の高精度分析装置と比較して非常に安価である。（製作単位によるものの百万円程度も可能である。）
Ｆ．上記効果Aにより、顧客に安心感を与えかつ信頼性を向上し得る。
By using the determination method described in claims 2 and 3 by the apparatus described in claim 1, in particular, the hydrogen fuel cell is used as a monitor, and the integrated power generation time T obtained from the determination reference data and the monitor measurement By comparing the measured value or change rate ΔV / ΔT of the cell voltage V with respect to real time in real time, the following effects can be expected. That is,
A. Since the hydrogen fuel property is constantly monitored, it can be immediately detected and dealt with immediately when it is out of the standard.
B. The hydrogen fuel cell for monitoring is MEA (Membrane).
If the Electrode Assembly = membrane / electrode assembly) is replaced, the entire monitoring device can be used continuously for a long period of time. The replacement frequency may be about once a year.
C. If the cell voltage change rate shows an abnormal value, if hydrogen containing several percent of oxygen is introduced and the cell voltage change rate recovers, it is caused by CO, and if it does not return, other components such as sulfur As a cause, it is possible to identify an impurity substance.
D. By appropriately changing the discrimination reference data, it can be used not only as a hydrogen property monitor but also as a device that can easily inspect the performance of a fuel cell with different specifications before shipment as a product.
E. It is very cheap compared with the conventional high precision analyzer. (Millions of yen are possible depending on the production unit.)
F. The above effect A can give the customer a sense of security and improve reliability.
本発明使用の主目的である水素燃料性状モニターに関する好ましい実施の形態について添付図面を参照しながら以下に説明する。図２は、本発明の実施の形態に係る水素燃料電池のセル電圧モニター装置のシステム構成図である。また図３は、水素ステーションにおける上記モニター装置の設置例図である。 A preferred embodiment relating to a hydrogen fuel property monitor which is the main purpose of the present invention will be described below with reference to the accompanying drawings. FIG. 2 is a system configuration diagram of a cell voltage monitoring device for a hydrogen fuel cell according to an embodiment of the present invention. FIG. 3 is an installation example of the monitoring device in the hydrogen station.
請求項１の発明に係る実施形態の場合について図２のセル電圧モニター装置を参照して具体的に説明する。セル電圧モニター装置は、管理する高純度の水素を逆止弁１５に通した後に加湿器３で加湿してモニター用水素燃料電池（以下、燃料電池セルと称す）４に送入する水素モニターラインＬ2と、空気を空気ブロア1で送入し、フィルタ２で除塵し、加湿器３で加湿して燃料電池セル４に送入する送気ラインＬ5と、弁１６に通した後に前記逆止弁１５と、加湿器３の間の水素モニターラインＬ2に酸素を供給するための酸素補給管17と、交換可能な標準ＭＥＡ（膜／電極接合体）５を組み込んだ前記燃料電池セル４と、管理する水素と空気を用いて燃料電池セル４で発電し、発電した電力を定電流で消費する定電流負荷器１１と、積算発電時間を測定するアワーメータ１２及びセル電圧を測定する電圧計１３と、その積算発電時間とセル電圧を入力し後述する水素燃料性状の判別基準データと比較して、管理する水素が正常か異常かを判別してそれを出力する記憶演算器１４と、水素燃料性状表示部１８と、燃料電池セル４から出る未利用の空気をラジエータ６で冷却しドレンタンク７で水分を分離して空気を排出する排気ラインと、燃料電池４からの未利用水素をラジエータ６で冷却しドレンタンク７で水を分離して、水素循環ブロア８で未利用水素を循環する循環ラインＬ3と、循環水素を定期的に弁９でパージするパージラインＬ4と、ドレンタンク７からの水を水ポンプ１０で燃料電池セル４の冷却部に送入して燃料電池セル４の発熱を制御し、暖められた水を加湿器３の加湿に利用する水ラインL６の各要素部材で構成される。 The case of the embodiment according to the invention of claim 1 will be specifically described with reference to the cell voltage monitoring device of FIG. The cell voltage monitor device is a hydrogen monitor line that passes high-purity hydrogen to be controlled through a check valve 15 and then humidifies it with a humidifier 3 and sends it to a monitoring hydrogen fuel cell (hereinafter referred to as a fuel cell) 4. L2 and air are fed by an air blower 1, dust is removed by a filter 2, humidified by a humidifier 3 and fed to a fuel cell 4, and the check valve after passing through a valve 16. 15, the oxygen supply pipe 17 for supplying oxygen to the hydrogen monitor line L 2 between the humidifier 3, the fuel cell 4 incorporating a replaceable standard MEA (membrane / electrode assembly) 5, and management A constant current loader 11 that generates power in the fuel cell 4 using hydrogen and air that is consumed and consumes the generated power at a constant current; an hour meter 12 that measures the accumulated power generation time; and a voltmeter 13 that measures the cell voltage; Enter the accumulated power generation time and cell voltage Comparing with reference data for determining the hydrogen fuel properties, which will be described later, it is determined whether the hydrogen to be managed is normal or abnormal, and the storage arithmetic unit 14 for outputting it, the hydrogen fuel property display section 18, and the fuel cell 4 are output. An exhaust line that cools unused air with a radiator 6, separates moisture with a drain tank 7 and discharges air, and cools unused hydrogen from the fuel cell 4 with a radiator 6 and separates water with a drain tank 7. The hydrogen circulation blower 8 circulates unused hydrogen, the purge line L4 that periodically purges the circulating hydrogen with the valve 9, and the water from the drain tank 7 cools the fuel cell 4 with the water pump 10. It is configured by each element member of the water line L6 that is fed into the unit to control the heat generation of the fuel cell 4 and uses the warmed water for humidification of the humidifier 3.
上記セル電圧モニター装置は、未利用水素を循環する循環ラインＬ3とパージラインＬ4を備える。導入・普及が予想される水素燃料電池自動車の場合においては、水素の利用率を向上させるために未利用水素を循環する。これは水素の利用率を向上させる一方、循環することにより水素燃料中の不純物が濃縮し、自動車の燃料電池に悪影響を及ぼす。そのため、水素燃料電池自動車は水素燃料中の不純物がある程度濃縮された時点で、その循環水素をパージする機構を設けることになる。従って本発明に係るセル電圧モニター装置は、当該モニター装置に未利用水素を循環する循環ラインＬ３とパージラインＬ4を設け、パージ頻度を調整できる機能を付加することにより、水素燃料電池自動車の燃料電池と同等の不純物が濃縮する条件を前記セル電圧モニター装置の燃料電池セル４に付与し、水素燃料性状の管理を適切に行うことができるようにするものである。 The cell voltage monitoring device includes a circulation line L3 and a purge line L4 for circulating unused hydrogen. In the case of hydrogen fuel cell vehicles that are expected to be introduced and spread, unused hydrogen is circulated in order to improve the utilization rate of hydrogen. While this improves the utilization rate of hydrogen, the impurities in the hydrogen fuel are concentrated by circulation, which adversely affects the fuel cell of the automobile. Therefore, the hydrogen fuel cell vehicle is provided with a mechanism for purging the circulating hydrogen when impurities in the hydrogen fuel are concentrated to some extent. Therefore, the cell voltage monitoring device according to the present invention is provided with a circulation line L3 and a purge line L4 for circulating unused hydrogen in the monitoring device, and by adding a function capable of adjusting the purge frequency, the fuel cell of the hydrogen fuel cell vehicle The conditions for concentrating impurities equivalent to the above are given to the fuel cell 4 of the cell voltage monitoring device so that the hydrogen fuel property can be appropriately managed.
本発明に係る上記セル電圧モニター装置の設置位置は、図３に例示されるように水素を利用する装置（この場合、水素燃料電池自動車）の直近であるディスペンサー出口の水素供給ラインＬ1に連接した水素モニターラインＬ2を選定して、水素利用側とモニター側とをできるだけ同じ条件にすることが望ましい。 The installation position of the cell voltage monitoring device according to the present invention is connected to a hydrogen supply line L1 at the outlet of the dispenser that is closest to the device using hydrogen (in this case, a hydrogen fuel cell vehicle) as illustrated in FIG. It is desirable to select the hydrogen monitor line L2 so that the hydrogen utilization side and the monitor side are as identical as possible.
本発明に係る上記セル電圧モニター装置において、図４を参照して、記憶演算器１４について説明する。この記憶演算器１４は、実測値を記憶するメモリー１４a及び判別基準データを記憶する記憶手段１４ｂと、実測値と判別基準データを比較判断するプログラムを記憶する記憶手段１４dと、実測値と判断基準データをメモリー１４dのプログラムに基づき演算する演算手段１４ｃとを備えている。メモリー１４ａは、アワーメータ１２で測定した積算発電時間Ｔと電圧計１３で測定したセル電圧Ｖとを記憶する例えばＲＡＭ１からなる。メモリー１４ｂは、水素燃料性状の正常・異常の状態を判別する要素としての判別基準データを記憶する例えばＲＡＭ２からなる。演算手段１４ｃは、両メモリー１４ａ，１４ｂのデータを、例えばＲＯＭからなるメモリー１４ｄに記憶される比較判断プログラムに基づき、演算・対比して判断を行う例えばＣＰＵからなるから成っていて、この演算結果に基づいて判断結果を表示部に表示させると同時に、警報を発信させ、制御対象の弁を開閉作動させるようになっている。 In the cell voltage monitoring apparatus according to the present invention, the storage arithmetic unit 14 will be described with reference to FIG. The storage computing unit 14 includes a memory 14a for storing actual measurement values, a storage unit 14b for storing discrimination reference data, a storage unit 14d for storing a program for comparing and determining actual measurement values and discrimination reference data, and actual measurement values and determination criteria. Computation means 14c for computing data based on a program in the memory 14d is provided. The memory 14 a includes, for example, a RAM 1 that stores the accumulated power generation time T measured by the hour meter 12 and the cell voltage V measured by the voltmeter 13. The memory 14b includes, for example, a RAM 2 that stores discrimination reference data as an element for discriminating whether the hydrogen fuel property is normal or abnormal. The computing means 14c is composed of, for example, a CPU that performs judgment by comparing and comparing the data in both memories 14a, 14b based on a comparison judgment program stored in a memory 14d, for example, a ROM. Based on the above, the determination result is displayed on the display unit, and at the same time, an alarm is issued to open and close the valve to be controlled.
上記判断基準データは、セル電圧モニター装置で実際に使用されるモニター用水素燃料電池と同一仕様の燃料電池に純水素及び規格値下限水素を流すことで採取される積算発電時間Ｔとセル電圧Vの値とをメモリー１４bに記憶することで取得できる。ここで図２を参照して、判断基準データの取得方法について具体的に説明する。始めにモニター用水素燃料電池４と同一仕様の水素燃料電池に対して、純水素及び水素燃料規格値下限の水素の２種を用いての前記定電流負荷回路１１による負荷テストを行わせて得られる、積算発電時間Ｔiとセル電圧Ｖiが計測され、メモリー１４aからＣＰＵ１４ｃを経由してメモリー１４bに積算発電時間Ｔiとセル電圧Ｖiが記憶される。記憶された積算発電時間Ｔiとセル電圧Ｖiのデータは、純水素である場合のセル電圧で表される許容上限値Ｖnと、水素燃料規格値下限の水素である場合のセル電圧で表される許容下限値Ｖaをそれぞれ水素燃料性状判別基準データとして設定される。この時同時に積算発電時間Ｔに対応する設定時点における変化率ΔV／ΔTがメモリー１４ｄのプログラムに基づきＣＰＵ１４ｃで演算されメモリー１４ｂに許容変化率として設定される。尚、このセル電圧経時変化を積算発電時間Ｔに対するセル電圧Ｖとしてプロットすると、図1のように傾きの小さい純水素の場合のセル電圧経時変化線と傾きの大きい水素燃料規格値下限水素の場合のセル電圧経時変化線のように模式的に表現でき、２つのセル電圧変化線に挟まれた網掛け部分は積算発電時間Ｔに対する正常なセル電圧Ｖの範囲を示している。
上記のようにして採取されたモニター用水素燃料電池の判別基準データは、同一仕様のセル電圧モニター装置間であれば共有することができる。従って、仕様が異なる複数のモニター用水素燃料電池の判別基準データを予め採取しておけば、モニター用水素燃料電池が変更になった場合であっても、判別基準データを変更するだけで容易に異なる仕様のセル電圧モニターに対応することができる。
尚、判別基準データの採取にあたっては、上記のように単純に水素を透過させて積算発電時間に対するセル電圧を測定する場合と、判別基準データの測定時間の短縮を図る為、水素内の不純物量や透過水素量を所定量変化させた加速試験を行う場合がある。
The above judgment reference data includes the accumulated power generation time T and the cell voltage V that are collected by flowing pure hydrogen and standard value lower limit hydrogen into a fuel cell having the same specifications as the monitoring hydrogen fuel cell actually used in the cell voltage monitoring device. Can be obtained by storing the value in the memory 14b. Here, with reference to FIG. 2, a method for acquiring the determination reference data will be specifically described. First, a hydrogen fuel cell having the same specifications as the monitoring hydrogen fuel cell 4 is subjected to a load test by the constant current load circuit 11 using two kinds of hydrogen, pure hydrogen and hydrogen at the lower limit of the hydrogen fuel standard value. The accumulated power generation time Ti and the cell voltage Vi are measured, and the accumulated power generation time Ti and the cell voltage Vi are stored in the memory 14b from the memory 14a via the CPU 14c. The stored accumulated power generation time Ti and cell voltage Vi data are expressed as an allowable upper limit value Vn expressed by a cell voltage when pure hydrogen is used and a cell voltage when hydrogen is a hydrogen fuel standard value lower limit. The allowable lower limit value Va is set as the hydrogen fuel property determination reference data. At the same time, the change rate ΔV / ΔT at the set time corresponding to the integrated power generation time T is calculated by the CPU 14c based on the program in the memory 14d and set as the allowable change rate in the memory 14b. When the cell voltage change with time is plotted as the cell voltage V with respect to the integrated power generation time T, the cell voltage change line with a small slope of pure hydrogen and the hydrogen fuel standard lower limit hydrogen with a large slope as shown in FIG. The shaded portion between the two cell voltage change lines indicates the range of the normal cell voltage V with respect to the accumulated power generation time T.
The discrimination reference data of the monitoring hydrogen fuel cell collected as described above can be shared between cell voltage monitoring devices of the same specification. Therefore, if the discrimination reference data for a plurality of monitor hydrogen fuel cells having different specifications are collected in advance, even if the monitor hydrogen fuel cell is changed, it is easy to change the discrimination reference data. It can support cell voltage monitors with different specifications.
In collecting the discrimination standard data, the amount of impurities in hydrogen is used to measure the cell voltage with respect to the accumulated power generation time by simply passing hydrogen as described above, and to reduce the measurement time of the discrimination standard data. In some cases, an accelerated test is performed by changing the permeated hydrogen amount by a predetermined amount.
請求項２の発明に係る実施形態の場合における記憶演算器１４の作動態様について図６を参照して具体的に説明する。本装置を判別モードに切替えて、積算発電時間Ｔｉに対するセル電圧値Viは１４ａ（ステップＳ１）から，積算発電時間Ｔｉに対応する判別基準データ基準値Ｖｎ，Ｖａは１４ｂから読み出して、積算発電時間Ｔｉに対する測定電圧値Ｖiが正常か異常かの判断を演算手段１４ｃで行わせ（ステップＳ３）、図5に拡大示されるようにＶa＜Ｖi＜Ｖｎであれば適正範囲にある、即ち、水素燃料性状が正常値と判定して次ステップに移行させ、Ｖｉ＜Ｖaであれば異常範囲にある、即ち、水素燃料性状が異常値であると判定して異常発生の表示を行わせる（ステップＳ４）。この時、図３に示す水素ステーションから水素燃料電池自動車への水素供給は中止する。 The operation mode of the storage computing unit 14 in the case of the embodiment according to the invention of claim 2 will be specifically described with reference to FIG. By switching this apparatus to the discrimination mode, the cell voltage value Vi for the integrated power generation time Ti is read from 14a (step S1), the discrimination reference data reference values Vn and Va corresponding to the integrated power generation time Ti are read from 14b, and the integrated power generation time Whether the measured voltage value Vi with respect to Ti is normal or abnormal is determined by the calculation means 14c (step S3), and as Va <Vi <Vn, as shown in an enlarged view in FIG. If the property is determined to be a normal value, the process proceeds to the next step. If Vi <Va, it is in the abnormal range, that is, the hydrogen fuel property is determined to be an abnormal value, and an abnormality is displayed (step S4). . At this time, the supply of hydrogen from the hydrogen station shown in FIG. 3 to the hydrogen fuel cell vehicle is stopped.
次に、請求項３の発明に係る実施形態についてΔＶi／ΔＴiの算出説明図である図５及び図６を参照して具体的に説明する。上記燃料性状が正常な場合（Ｖa＜Ｖi＜Ｖｎ）において、積算発電時間Ｔiに対するセル電圧Ｖiをメモリー１４ａから、積算発電時間Ｔiに対応する設定時点における許容変化率ΔＶａ／ΔＴａを１４ｂから読み出し、演算手段１４ｃでモニター実測から変化率ΔＶｉ／ΔＴｉの演算（ステップＳ６）を行い、許容変化率ΔＶａ／ΔＴａと比較して該変化率ΔＶｉ／ΔＴｉの正常・異常の判断を行わせる（ステップＳ７）。この場合における変化率ΔＶｉ／ΔＴｉの演算は、図５に拡大示されるように設定した単位短時間に対するセル電圧の変化から求められる。尚、上記では許容変化率ΔＶａ／ΔＴａをメモリー１４bから読み出しているが、メモリー容量を抑える意味で、水素性状基準データのＶａ及びＴａから演算手段１４ｃにて逐次演算を行ってもよい。 Next, an embodiment according to the invention of claim 3 will be described in detail with reference to FIGS. 5 and 6 which are explanatory diagrams for calculating ΔVi / ΔTi. When the fuel property is normal (Va <Vi <Vn), the cell voltage Vi for the accumulated power generation time Ti is read from the memory 14a, and the allowable change rate ΔVa / ΔTa at the set time corresponding to the accumulated power generation time Ti is read from 14b. The calculation means 14c calculates the change rate ΔVi / ΔTi from the actual measurement of the monitor (step S6), and compares the change rate ΔVa / ΔTa with the allowable change rate ΔVa / ΔTa to determine whether the change rate ΔVi / ΔTi is normal or abnormal (step S7). . The calculation of the change rate ΔVi / ΔTi in this case is obtained from the change in the cell voltage with respect to the unit short time set as shown in an enlarged view in FIG. In the above description, the allowable change rate ΔVa / ΔTa is read from the memory 14b. However, in order to reduce the memory capacity, the calculation means 14c may sequentially calculate the hydrogen property reference data Va and Ta.
変化率ΔＶｉ／ΔＴｉと許容変化率ΔＶａ／ΔＴａを演算手段１４ｃで対比させ、｜ΔＶｉ／ΔＴｉ｜≦｜ΔＶａ／ΔＴａ｜であれば水素燃料性状は正常と判定して次ステップのモニター継続に移行させ（ステップＳ２０）、｜ΔＶｉ／ΔＴｉ｜＞｜ΔＶａ／ΔＴａ｜であれば燃料性状が悪化すると予測して、水素燃料性状異常発生を表示させる（ステップＳ８）。この時、図３に示す水素供給ステーションから水素燃料電池自動車への水素供給は中止する。次段階のセル電圧復旧ルーチンへの移行（ステップＳ９）は、水素燃料性状の悪化がどの不純物によるものかを究明するために用いられる。 The rate of change ΔVi / ΔTi and the allowable rate of change ΔVa / ΔTa are compared by the calculation means 14c. If | ΔVi / ΔTi | ≦ | ΔVa / ΔTa |, the hydrogen fuel property is determined to be normal, and the process proceeds to the next step of monitoring. (Step S20), if | ΔVi / ΔTi |> | ΔVa / ΔTa |, the fuel property is predicted to deteriorate, and the occurrence of hydrogen fuel property abnormality is displayed (Step S8). At this time, the hydrogen supply from the hydrogen supply station shown in FIG. 3 to the hydrogen fuel cell vehicle is stopped. The transition to the cell voltage recovery routine at the next stage (step S9) is used to investigate which impurities are responsible for the deterioration in hydrogen fuel properties.
請求項４の発明に係る実施形態について図５及び図６並びにセル電圧復旧制御の手順を示すフロー図である図７を参照して具体的に説明する。変化率が｜ΔＶｉ／ΔＴｉ｜＞｜ΔＶａ／ΔＴａ｜であって水素燃料性状の悪化を予測すると次段階のセル電圧復旧ルーチンに移行させ（ステップＳ９）、セル電圧復旧ルーチンの開始時刻Ｔｓを計測後に（ステップＳ２１）、酸素を供給する（ステップＳ２２）。即ち、高純度水素中の酸素濃度が所定濃度になるように、水素モニターラインＬ２を通じて酸素をモニター用水素燃料電池４に送入させてセル電圧の回復を図らせるようにするのである。 The embodiment according to the invention of claim 4 will be described in detail with reference to FIGS. 5 and 6 and FIG. 7 which is a flowchart showing the procedure of the cell voltage recovery control. If the rate of change is | ΔVi / ΔTi |> | ΔVa / ΔTa | and the deterioration of the hydrogen fuel property is predicted, the cell voltage recovery routine is shifted to the next stage (step S9), and the start time Ts of the cell voltage recovery routine is measured. Later (step S21), oxygen is supplied (step S22). That is, oxygen is sent to the monitoring hydrogen fuel cell 4 through the hydrogen monitor line L2 so that the cell voltage can be recovered so that the oxygen concentration in the high purity hydrogen becomes a predetermined concentration.
演算手段１４ｃにおけるセル電圧復旧作動の手順は図７のステップＳ１１〜ステップＳ１７、ステップＳ２３〜ステップＳ２６に示される通りであって、酸素の供給に基づいて｜ΔＶｉ／ΔＴｉ｜≦｜ΔＶａ／ΔＴａ｜となり正常に復したと判断された際には、酸素供給を停止する（ステップＳ２３）。また、｜ΔＶｉ／ΔＴｉ｜＞｜ΔＶａ／ΔＴａ｜の異常状態の継続時間Ｔｍ−Ｔｓが所定時間Ｔｐに達しない間は酸素供給を続け、継続時間が所定時間Ｔpに達してもなお異常値が継続する場合は「ＭＥＡ交換表示」を行いモニターを終了する。 The procedure of the cell voltage recovery operation in the computing means 14c is as shown in Steps S11 to S17 and Steps S23 to S26 of FIG. 7, and based on the supply of oxygen, | ΔVi / ΔTi | ≦ | ΔVa / ΔTa | When it is determined that the normal state has been restored, the oxygen supply is stopped (step S23). Further, the oxygen supply is continued while the duration time Tm-Ts of the abnormal state of | ΔVi / ΔTi |> | ΔVa / ΔTa | does not reach the predetermined time Tp, and the abnormal value still remains even when the duration reaches the predetermined time Tp. When continuing, "MEA exchange display" is performed and the monitor is terminated.
本発明によれば水素燃料中の不純物種を特定できる。その判断の一例を挙げると、ＣＯが規格値下限以上であっても、酸素を付加することでセル電圧は積算時間Ｔｉに対応するセル電圧Ｖｉ付近まで回復する。しかしながら、硫黄化合物が規格値下限以上であれば、酸素を付加しても、セル電圧は回復することはない。従って、実際の水素供給設備にモニターを設置し、水素性状の異常を検知した場合に、上記所定濃度の酸素を付加してセル電圧の経時変化を採取すれば、規格値下限以上である不純物がＣＯであるのか硫黄であるのかを判別できる。例えば図３において、水素燃料性状の異常がＣＯであると判別した場合は水素精製装置を、水素燃料性状の異常が硫黄であると判別した場合は改質器に組込まれている脱硫装置を点検、修理もしくは薬剤交換等の措置を講じれば良く、異常発生箇所の特定が可能となる。 According to the present invention, the impurity species in the hydrogen fuel can be specified. As an example of the determination, even if CO is equal to or higher than the lower limit of the standard value, the cell voltage is recovered to the vicinity of the cell voltage Vi corresponding to the integration time Ti by adding oxygen. However, if the sulfur compound is at least the lower limit of the standard value, the cell voltage will not recover even if oxygen is added. Therefore, when a monitor is installed in an actual hydrogen supply facility and an abnormality in the hydrogen property is detected, if the change over time in the cell voltage is collected by adding oxygen at the predetermined concentration, impurities exceeding the lower limit of the standard value can be obtained. Whether it is CO or sulfur can be determined. For example, in FIG. 3, when it is determined that the abnormality in the hydrogen fuel property is CO, the hydrogen purifier is inspected. When it is determined that the abnormality in the hydrogen fuel property is sulfur, the desulfurization device incorporated in the reformer is inspected. Then, it is sufficient to take measures such as repair or drug replacement, and it is possible to identify the location where an abnormality has occurred.
本発明は上記で説明したような水素燃料性状モニターに留まらず、水素燃料電池の性能検査の装置及び検査方法として使用できる。すなわち、請求項５の発明に係る実施形態について図５を参照して具体的に説明すると、性能検査対象となる燃料電池を請求項１に示すセル電圧モニター装置に接続し、水素モニターする場合と同様にして性能検査用規格水素燃料を一定時間流通させ、積算発電時間Ｔ０とセル電圧Ｖ０を測定する。そして、セル電圧Ｖ０が図５において許容上限値線（Ｖｎ）と許容下限値線（Ｖa）の間に挟まれた網掛部内にあれば正常、そうでなければ異常と判断する。正常であれば継続して水素燃料を流通させ、図６に示すようにT１における変化率ΔV１／ΔT１が一定時間経過後の積算発電時間Ｔ２において｜ΔＶ２／ΔＴ２｜＜｜ΔＶａ／ΔＴa｜であれば検査した燃料電池を合格とし、積算発電時間Ｔ２における変化率が｜ΔV3／ΔT２｜＞｜ΔＶa／ΔＴa｜であれば検査した燃料電池を不良と判断する。この方法によれば、簡単かつ比較的短時間で燃料電池を検査することが可能である。また、仕様が異なる燃料電池の判別基準データを予め複数準備しておけば、判別基準データを変更するだけで仕様の異なる燃料電池の検査を容易に行うことができる。 The present invention is not limited to the hydrogen fuel property monitor as described above, but can be used as an apparatus and a method for inspecting the performance of a hydrogen fuel cell. That is, the embodiment according to the invention of claim 5 will be described in detail with reference to FIG. 5. The fuel cell to be performance-tested is connected to the cell voltage monitor device shown in claim 1 for hydrogen monitoring. Similarly, the standard hydrogen fuel for performance inspection is allowed to flow for a certain time, and the accumulated power generation time T0 and the cell voltage V0 are measured. Then, if the cell voltage V0 is within the shaded portion sandwiched between the allowable upper limit value line (Vn) and the allowable lower limit value line (Va) in FIG. If normal, hydrogen fuel is continuously circulated, and as shown in FIG. 6, the rate of change ΔV1 / ΔT1 in T1 may be | ΔV2 / ΔT2 | <| ΔVa / ΔTa | If the change rate in the accumulated power generation time T2 is | ΔV3 / ΔT2 |> | ΔVa / ΔTa |, the checked fuel cell is determined to be defective. According to this method, it is possible to inspect the fuel cell easily and in a relatively short time. If a plurality of discrimination reference data for fuel cells having different specifications are prepared in advance, it is possible to easily inspect fuel cells having different specifications simply by changing the discrimination reference data.
１…空気ブロア、２…フィルタ、３…加湿器、４…モニター用水素燃料電池、５…ＭＥＡ（膜／電極接合体）、６…ラジエータ、７…ドレンタンク、８…水素循環ブロア、９…弁、１０…水ポンプ、１１…定電流負荷回路、１２…アワーメータ、１３…電圧計、１４…記憶演算器、１５…逆止弁、１６…弁、１７…酸素補給管、１８…水素燃料性状表示部、１９…排気ライン、Ｌ1…水素供給ライン、Ｌ2…水素モニターライン、Ｌ3…循環ライン、Ｌ4…パージライン、Ｌ5…送気ライン、Ｌ6…水ライン。 DESCRIPTION OF SYMBOLS 1 ... Air blower, 2 ... Filter, 3 ... Humidifier, 4 ... Monitoring hydrogen fuel cell, 5 ... MEA (membrane / electrode assembly), 6 ... Radiator, 7 ... Drain tank, 8 ... Hydrogen circulation blower, 9 ... Valves, 10 ... water pump, 11 ... constant current load circuit, 12 ... hour meter, 13 ... voltmeter, 14 ... memory calculator, 15 ... check valve, 16 ... valve, 17 ... oxygen supply pipe, 18 ... hydrogen fuel Property display section, 19 ... exhaust line, L1 ... hydrogen supply line, L2 ... hydrogen monitor line, L3 ... circulation line, L4 ... purge line, L5 ... air supply line, L6 ... water line.
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