JP2017162573A - Method for measuring electrical characteristics of fuel battery cell, and method for diagnosing fuel battery cell stack - Google Patents

Method for measuring electrical characteristics of fuel battery cell, and method for diagnosing fuel battery cell stack Download PDF

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JP2017162573A
JP2017162573A JP2016043774A JP2016043774A JP2017162573A JP 2017162573 A JP2017162573 A JP 2017162573A JP 2016043774 A JP2016043774 A JP 2016043774A JP 2016043774 A JP2016043774 A JP 2016043774A JP 2017162573 A JP2017162573 A JP 2017162573A
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single cell
cell
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賢志 安井
Kenji Yasui
賢志 安井
古川　英夫
Hideo Furukawa
英夫 古川
靖国 田中
Yasukuni Tanaka
靖国 田中
岡本　崇
Takashi Okamoto
崇 岡本
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Miura Co 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
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Abstract

PROBLEM TO BE SOLVED: To provide a method for measuring electrical characteristics of a fuel battery cell and a method for diagnosing a fuel battery cell stack, capable of being utilized for soundness evaluation of a cell stack of a solid oxide fuel cell.SOLUTION: A method for measuring electrical characteristics of a fuel battery cell includes: a charging curve recording step of recording time change of a charging voltage value of an arbitrary single cell 201 as a charge curve by connecting a first external resistor 12 having a first resistance value and a constant voltage DC power supply 11 to the single cell 201 to form a charging circuit A1 under the normal temperature in which a fuel cell 200 does not perform power generation; an internal resistance value measuring step of measuring an internal resistance value of the single cell 201 based on a first resistance value, a value of DC voltage applied to the constant voltage DC power supply 11, and a full charge voltage value of the single cell 201 obtained by the charge curve; and a static capacitance value measurement step of measuring a static capacitance value of the single cell 201 based on time constant of the single cell 201 obtained by the charge curve, and the internal resistance value.SELECTED DRAWING: Figure 1

Description

本発明は、燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法に関する。   The present invention relates to a method for measuring electric characteristics of a fuel cell and a method for diagnosing a fuel cell stack.

固体酸化物形燃料電池（ＳＯＦＣ）は、複数の単セルが積層されたセルスタック構造を有している。セルスタックは、平板構造と円筒構造に大別されるが、いずれの場合もアノード（燃料極）、カソード（空気極）、及び電解質からなるセラミックス製の単セルがインターコネクタを介して連結された構造を有している。セルスタックに組み込まれた各単セルにおいては、アノード側に水素含有燃料を、カソード側に空気を供給し、内部で水素と酸素を反応させることにより発電が行われる。   A solid oxide fuel cell (SOFC) has a cell stack structure in which a plurality of single cells are stacked. The cell stack is roughly divided into a flat plate structure and a cylindrical structure. In each case, a single cell made of ceramics composed of an anode (fuel electrode), a cathode (air electrode), and an electrolyte is connected via an interconnector. It has a structure. In each single cell incorporated in the cell stack, power generation is performed by supplying hydrogen-containing fuel on the anode side and air on the cathode side and reacting hydrogen and oxygen inside.

ところで、燃料電池の製造工場で組立・焼成・還元処理されたセルスタックにおいて、製造工程などに起因して異質な単セルが所定割合以上含まれている場合、所期の発電能力を発揮できない。セルスタックの発電能力が不足していると、必要な電力を需要箇所に供給できないことから、単セルの健全性を診断する方法（特許文献１，２）やセルスタックの健全性を診断する方法（特許文献３）が提案されている。   By the way, in a cell stack that has been assembled, fired, and reduced at a fuel cell manufacturing factory, if the number of heterogeneous single cells is greater than or equal to a predetermined ratio due to the manufacturing process, the desired power generation capacity cannot be exhibited. A method for diagnosing the health of a single cell (Patent Documents 1 and 2) and a method for diagnosing the health of a cell stack because the required power cannot be supplied to a demand point if the power generation capacity of the cell stack is insufficient (Patent Document 3) has been proposed.

特開２００７−２１４０７２号公報JP 2007-214072 A 特開２００８−１６６１８９号公報JP 2008-166189 A 特開２００４−２４１３２５号公報JP 2004-241325 A

固体酸化物形燃料電池のセルスタックは、発電中の動作温度が高く、その温度は６００〜１０００℃にも達する。そのため、燃料電池ユニットの起動後にセルスタックの発電能力の不足が判明した場合には、一旦運転を停止し、セルスタックの温度が下がるのを待ってから新たなセルスタックに交換するなどの必要が生じる。しかも、セルスタックの交換中は、需要箇所に電力を供給できない上、単セルやセルスタックの健全性の診断を燃料電池ユニットの設置現場で行うのは困難である。このような事情から、燃料電池ユニットを作動させる前に、単セルやセルスタックの健全性評価を行うことが望まれていた。   The cell stack of a solid oxide fuel cell has a high operating temperature during power generation, and the temperature reaches 600 to 1000 ° C. Therefore, if it becomes clear that the power generation capacity of the cell stack is insufficient after starting the fuel cell unit, it is necessary to stop the operation once and wait for the temperature of the cell stack to drop before replacing it with a new cell stack. Arise. In addition, during replacement of the cell stack, it is difficult to supply power to the demand point, and it is difficult to diagnose the soundness of the single cell or the cell stack at the installation site of the fuel cell unit. Under such circumstances, it has been desired to evaluate the soundness of single cells and cell stacks before operating the fuel cell unit.

本発明は、固体酸化物形燃料電池のセルスタックの健全性評価に利用することのできる燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法を提供することを目的とする。   It is an object of the present invention to provide a method for measuring the electrical characteristics of a fuel cell and a method for diagnosing the fuel cell stack that can be used for the evaluation of the soundness of a cell stack of a solid oxide fuel cell.

本発明は、固体酸化型燃料電池のセルスタックにおいて、前記燃料電池が発電を行っていない常温下で、任意の単セルに対して第１抵抗値を有する第１外部抵抗、及び定電圧直流電源を接続して充電用回路を形成することにより、前記単セルの充電電圧値の時間変化を充電曲線として記録する充電曲線記録工程と、前記第１抵抗値、前記定電圧直流電源により印加した直流電圧値、及び前記充電曲線より求めた前記単セルの満充電電圧値に基づいて、前記単セルの内部抵抗値を算出する内部抵抗値算出工程と、前記充電曲線より求めた前記単セルの時定数、及び前記内部抵抗値に基づいて、前記単セルの静電容量値を算出する静電容量値算出工程と、を含む燃料電池セルの電気特性測定方法に関する。   In the cell stack of a solid oxide fuel cell, the present invention provides a first external resistor having a first resistance value with respect to an arbitrary single cell and a constant voltage DC power source at room temperature where the fuel cell is not generating power. Are connected to form a charging circuit to record a time change in the charging voltage value of the single cell as a charging curve, and a direct current applied by the first resistance value and the constant voltage DC power source. An internal resistance value calculating step for calculating an internal resistance value of the single cell based on a voltage value and a full charge voltage value of the single cell determined from the charging curve, and a time of the single cell determined from the charging curve. And a capacitance value calculating step of calculating a capacitance value of the single cell based on a constant and the internal resistance value.

また、本発明は、固体酸化型燃料電池のセルスタックにおいて、前記燃料電池が発電を行っていない常温下で、任意の単セルに対して第１抵抗値を有する第１外部抵抗、及び定電圧直流電源を接続して充電用回路を形成することにより、前記単セルの充電電圧値の時間変化を充電曲線として記録した後、前記定電圧直流電源の接続を遮断して放電用回路を形成することにより、前記単セルの充電電圧値の時間変化を放電曲線として記録する充放電曲線記録工程と、前記第１抵抗値、前記定電圧直流電源により印加した直流電圧値、及び前記充電曲線より求めた前記単セルの満充電電圧値に基づいて、前記単セルの内部抵抗値を算出する内部抵抗値算出工程と、前記放電曲線より求めた前記単セルの時定数、及び前記内部抵抗値に基づいて、前記単セルの静電容量値を算出する静電容量値算出工程と、を含む燃料電池セルの電気特性測定方法に関する。   Further, according to the present invention, in a cell stack of a solid oxide fuel cell, a first external resistor having a first resistance value with respect to an arbitrary single cell and a constant voltage at room temperature when the fuel cell is not generating power. By forming a charging circuit by connecting a DC power supply, a time change in the charging voltage value of the single cell is recorded as a charging curve, and then the connection of the constant voltage DC power supply is cut off to form a discharging circuit. Thus, a charge / discharge curve recording step of recording a time change of the charging voltage value of the single cell as a discharge curve, the first resistance value, a DC voltage value applied by the constant voltage DC power source, and the charging curve are obtained. Based on the internal resistance value calculation step of calculating the internal resistance value of the single cell based on the full charge voltage value of the single cell, the time constant of the single cell obtained from the discharge curve, and the internal resistance value Before And the capacitance value calculation step of calculating the electrostatic capacitance value of the single cell, to an electrical characteristic measuring method of a fuel cell comprising a.

また、本発明は、前記電気特性測定方法に従って、前記セルスタックの単セルごとに前記内部抵抗値及び前記静電容量値を測定する電気特性測定工程と、前記単セルごとの前記内部抵抗値どうし、及び／又は、前記静電容量値どうしを比較し、前記セルスタックが特性の異なる前記単セルを含むか否かを判別する異特性セル判別工程と、を含む燃料電池セルスタックの診断方法に関する。   Further, the present invention provides an electrical property measuring step of measuring the internal resistance value and the capacitance value for each single cell of the cell stack according to the electrical property measurement method, and the internal resistance values for each single cell. And / or a different characteristic cell determination step of comparing the capacitance values and determining whether or not the cell stack includes the single cells having different characteristics. .

本発明によれば、固体酸化物形燃料電池のセルスタックの健全性評価に利用することのできる燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the electrical property measuring method of the fuel cell which can be utilized for the soundness evaluation of the cell stack of a solid oxide fuel cell, and the diagnostic method of a fuel cell stack can be provided.

本発明の燃料電池セルの電気特性測定方法において、単セルの充電用回路を形成した状態を示す回路図である。It is a circuit diagram which shows the state which formed the circuit for charge of the single cell in the electrical property measuring method of the fuel cell of this invention. 本発明の第１実施形態に係る単セルの充電曲線である。It is a charging curve of the single cell which concerns on 1st Embodiment of this invention. 本発明の第２実施形態に係る単セルの充電曲線及び放電曲線である。It is the charge curve and discharge curve of the single cell which concern on 2nd Embodiment of this invention.

以下、本発明の第１実施形態に係る燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法について説明する。先ず、燃料電池セルの電気特性測定方法で用いられる電気特性測定装置の回路の構成について図１を参照しながら説明する。図１は、電気特性測定装置において、単セルの充電用回路を形成した状態を示す回路図である。   Hereinafter, a method for measuring electric characteristics of a fuel cell and a method for diagnosing a fuel cell stack according to a first embodiment of the present invention will be described. First, the circuit configuration of an electrical characteristic measuring apparatus used in the method for measuring the electrical characteristics of a fuel cell will be described with reference to FIG. FIG. 1 is a circuit diagram showing a state in which a single-cell charging circuit is formed in an electrical characteristic measuring apparatus.

図１に示す電気特性測定装置１は、固体酸化型燃料電池２００のセルスタックを構成する単セル２０１の内部抵抗値及び静電容量値を測定するための装置である。発電装置として提供される燃料電池ユニットは、燃料電池２００、空気予熱器、水蒸発器、改質器、燃焼器等を断熱材で包囲したホットモジュールと、発電動作及び電力供給等に必要な補機群と、熱回収に使用する熱交換器と、をパッケージ化したものである。   An electrical property measuring apparatus 1 shown in FIG. 1 is an apparatus for measuring an internal resistance value and a capacitance value of a single cell 201 constituting a cell stack of a solid oxide fuel cell 200. The fuel cell unit provided as a power generation device includes a hot module in which the fuel cell 200, the air preheater, the water evaporator, the reformer, the combustor and the like are surrounded by a heat insulating material, and a supplement necessary for power generation operation and power supply. A machine group and a heat exchanger used for heat recovery are packaged.

電気特性測定装置１は、定電圧直流電源１１と、第１外部抵抗１２と、充電電圧測定器としての電圧計１３と、を有している。定電圧直流電源１１及び第１外部抵抗１２は、燃料電池２００が発電を行っていない常温下で、測定対象単セル２０１に電気的に直列接続され、測定対象単セル２０１を充電する充電用回路Ａ１を形成する。また、電圧計１３は、測定対象単セル２０１に電気的に並列接続される。   The electrical characteristic measuring apparatus 1 includes a constant voltage DC power source 11, a first external resistor 12, and a voltmeter 13 as a charging voltage measuring device. The constant voltage DC power supply 11 and the first external resistor 12 are electrically connected in series to the measurement target single cell 201 at room temperature where the fuel cell 200 is not generating power, and charging circuit for charging the measurement target single cell 201 A1 is formed. The voltmeter 13 is electrically connected in parallel to the measurement target single cell 201.

定電圧直流電源１１は、所定の直流電圧値Ｖ０（数ボルト程度）を充電用回路Ａ１に印加可能に構成されている。第１外部抵抗１２は、第１抵抗値Ｒ１を有しており、この第１抵抗値Ｒ１は、単セル２０１の内部抵抗値Ｒｉに基づいて設定される。典型的には、第１抵抗値Ｒ１は、単セル２０１の内部抵抗値Ｒｉの０．１〜１０倍程度に設定される。電圧計１３は、単セル２０１の２つの電極、即ち、カソードと、アノードとにそれぞれ電気的に接続され、単セル２０１の充電電圧値を測定可能である。 The constant voltage DC power supply 11 is configured to be able to apply a predetermined DC voltage value V 0 (about several volts) to the charging circuit A1. The first external resistor 12 has a first resistance value R 1 , and the first resistance value R 1 is set based on the internal resistance value R i of the single cell 201. Typically, the first resistance value R 1 is set to about 0.1 to 10 times the internal resistance value R i of the single cell 201. The voltmeter 13 is electrically connected to two electrodes of the single cell 201, that is, a cathode and an anode, respectively, and can measure a charging voltage value of the single cell 201.

次に、燃料電池セルの電気特性測定方法について図２を参照しながら説明する。図２は、単セル２０１の充電曲線である。第１実施形態に係る燃料電池セルの電気特性測定方法は、充電曲線記録工程と、内部抵抗値算出工程と、静電容量値算出工程と、を含んでいる。   Next, a method for measuring the electrical characteristics of the fuel cell will be described with reference to FIG. FIG. 2 is a charging curve of the single cell 201. The method for measuring the electrical characteristics of the fuel cell according to the first embodiment includes a charging curve recording step, an internal resistance value calculating step, and a capacitance value calculating step.

充電曲線記録工程では、燃料電池２００が発電を行っていない常温下で、任意の単セル２０１に対して、第１外部抵抗１２及び定電圧直流電源１１を接続して充電用回路Ａ１（図１参照）を形成することにより、単セル２０１の充電電圧値の時間変化を充電曲線Ｃ１として記録する。   In the charging curve recording step, the first external resistor 12 and the constant voltage DC power source 11 are connected to an arbitrary single cell 201 at room temperature where the fuel cell 200 is not generating power, and the charging circuit A1 (FIG. 1). The time change of the charging voltage value of the single cell 201 is recorded as a charging curve C1.

具体的には、充電曲線記録工程では、先ず、燃料電池２００が燃料電池ユニットに搭載されていない状態（典型的には、組立・焼成・還元処理済みセルスタックが出荷前の状態）で、測定対象単セル２０１に対して、上述した電気特性測定装置１を接続する。そして、測定対象単セル２０１に所定の直流電圧値Ｖ０を印加して充電を開始する。単セル２０１の充電中は、電圧計１３により充電曲線Ｃ１を記録し、充電電圧値が飽和した時点で満充電電圧値ＶＳに達したものと判断して充電操作を終了する。 Specifically, in the charging curve recording step, first, measurement is performed in a state where the fuel cell 200 is not mounted on the fuel cell unit (typically, the assembled / fired / reduced cell stack is in a state before shipment). The above-described electrical property measuring apparatus 1 is connected to the target single cell 201. Then, a predetermined DC voltage value V 0 is applied to the measurement target single cell 201 to start charging. During charging of the single cell 201, the charging curve C1 is recorded by the voltmeter 13, and when the charging voltage value is saturated, it is determined that the full charging voltage value V S has been reached, and the charging operation is terminated.

充電曲線記録工程に続く内部抵抗値算出工程では、第１抵抗値Ｒ１、定電圧直流電源１１により印加した直流電圧値Ｖ０、及び充電曲線Ｃ１より求めた測定対象単セル２０１の満充電電圧値ＶＳに基づいて、測定対象単セル２０１の内部抵抗値Ｒｉを算出する。具体的には、次の式（１）を使用して内部抵抗値Ｒｉを求める。なお、式（１）は、満充電時に単セル２０１に流れる電流値と第１外部抵抗１２に流れる電流値とが等しいという関係から導ける数式である。
Ｒｉ＝ＶＳ×Ｒ１÷（Ｖ０−ＶＳ） … （１） In the internal resistance value calculating step subsequent to the charging curve recording step, the full charge voltage of the measurement target single cell 201 obtained from the first resistance value R 1 , the DC voltage value V 0 applied by the constant voltage DC power supply 11, and the charging curve C 1. Based on the value V S , the internal resistance value R i of the measurement target single cell 201 is calculated. Specifically, the internal resistance value R i is obtained using the following equation (1). Equation (1) is an equation derived from the relationship that the current value flowing through the single cell 201 and the current value flowing through the first external resistor 12 are equal when fully charged.
R i = V S × R 1 ÷ (V 0 −V S ) (1)

内部抵抗値算出工程に続く静電容量値算出工程では、充電曲線Ｃ１より求めた測定対象単セル２０１の時定数τｉ、及び内部抵抗値Ｒｉに基づいて、測定対象単セル２０１の静電容量値Ｃｉを求める。具体的には、次の式（２）を使用して静電容量値Ｃｉを求める。
Ｃｉ＝τｉ÷Ｒｉ … （２） In the capacitance value calculation step subsequent to the internal resistance value calculation step, the electrostatic capacitance of the measurement target single cell 201 is determined based on the time constant τ i of the measurement target single cell 201 obtained from the charging curve C1 and the internal resistance value R i. The capacitance value C i is obtained. Specifically, the capacitance value C i is obtained using the following equation (2).
C i = τ i ÷ R i (2)

ここで、単セル２０１の時定数τｉは、充電終了時点の充電電圧値（すなわち、満充電電圧値ＶＳ）を１００％として、充電中の充電電圧値が満充電電圧値ＶＳの６３．２％（＝１−１／ｅ×１００）まで到達するのに要する時間である。図２の充電曲線Ｃ１に示すように、充電開始時刻をｔ１とし、充電電圧値がＶＳ×（１−１／ｅ）となった時刻をｔ２とすると、単セル２０１の時定数τｉは、次の式（３）で表わされる。
τｉ＝ｔ２−ｔ１ … （３） Here, the time constant τ i of the single cell 201 is such that the charging voltage value at the end of charging (that is, the full charging voltage value V S ) is 100%, and the charging voltage value during charging is 63 of the full charging voltage value V S. This is the time required to reach 2% (= 1−1 / e × 100). As shown in the charging curve C1 in FIG. 2, the charging start time and t 1, when the time at which the charging voltage value becomes V S × (1-1 / e) and t 2, the time constant of the unit cell 201 tau i is represented by the following equation (3).
τ i = t 2 −t 1 (3)

次に、燃料電池セルスタックの診断方法について説明する。第１実施形態に係る燃料電池セルスタックの診断方法は、上述した燃料電池セルの電気特性測定方法に従う電気特性測定工程と、異特性セル判別工程と、を含んでいる。電気特性測定工程では、内部抵抗値算出工程で求めた内部抵抗値Ｒｉ及び静電容量値算出工程で求めた静電容量値Ｃｉを取得し、単セルの異質性を判別するための情報として利用する。 Next, a fuel cell stack diagnosis method will be described. The fuel cell stack diagnostic method according to the first embodiment includes an electrical property measurement step according to the above-described electrical property measurement method for a fuel cell and a different property cell discrimination step. In the electrical characteristic measurement process, information for acquiring the internal resistance value R i obtained in the internal resistance value calculation process and the capacitance value C i obtained in the capacitance value calculation process and determining the heterogeneity of the single cell. Use as

電気特性測定工程に続く異特性セル判別工程では、単セル２０１ごとの内部抵抗値Ｒｉどうし、及び、静電容量値Ｃｉどうしを比較し、セルスタックが特性の異なる単セル２０１を含むか否かを判別する。そして、セルスタックが異質な単セル２０１を所定割合以上（例えば、全セル数に対して数％程度）含む場合には、セルスタックの健全性が担保されていないと判断し、当該セルスタックを燃料電池ユニットに搭載することなく補修する。補修が困難な場合は、再利用可能な部品を回収した後、廃棄等の処分を行ってもよい。
なお、異特性セル判別工程では、単セル２０１どうしの特性値を比較して異質性を判別するだけでなく、各単セル２０１の特性値を予め設定した基準値（例えば、全セルの特性値の平均値）と比較することにより、その異質性を判別してもよい。 In the different characteristic cell discrimination process following the electrical characteristic measurement process, whether the cell stack includes single cells 201 having different characteristics by comparing internal resistance values R i and capacitance values C i for each single cell 201. Determine whether or not. If the cell stack contains a single cell 201 of a different size or more than a predetermined ratio (for example, about several percent with respect to the total number of cells), it is determined that the soundness of the cell stack is not secured, and the cell stack is Repair without mounting on the fuel cell unit. When repair is difficult, after reusable parts are collected, disposal such as disposal may be performed.
In the different characteristic cell determination step, not only the characteristic values of the single cells 201 are compared to determine the heterogeneity but also the characteristic values of the single cells 201 are set in advance as reference values (for example, characteristic values of all cells). The heterogeneity may be discriminated by comparing with the average value.

第１実施形態に係る燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法によれば、以下のような効果を得ることができる。   According to the method for measuring the electrical characteristics of the fuel cell and the diagnostic method for the fuel cell stack according to the first embodiment, the following effects can be obtained.

燃料電池セルの電気特性測定方法は、固体酸化型燃料電池のセルスタックにおいて、燃料電池２００が発電を行っていない常温下で、任意の単セル２０１に対して第１抵抗値Ｒ１を有する第１外部抵抗１２、及び定電圧直流電源１１を接続して充電用回路Ａ１を形成することにより、単セル２０１の充電電圧値の時間変化を充電曲線Ｃ１として記録する充電曲線記録工程と、第１抵抗値Ｒ１、定電圧直流電源１１により印加した直流電圧値Ｖ０、及び充電曲線Ｃ１より求めた満充電電圧値ＶＳに基づいて、単セル２０１の内部抵抗値Ｒｉを算出する内部抵抗値算出工程と、充電曲線Ｃ１より求めた単セル２０１の時定数τｉ、及び内部抵抗値Ｒｉに基づいて、単セル２０１の静電容量値Ｃｉを算出する静電容量値算出工程と、を含む。このため、燃料電池ユニットを作動させる前に、セルスタックの全体に亘って単セル２０１の内部抵抗値Ｒｉ及び静電容量値Ｃｉを正確且つ短時間で計測ことができる。 In the cell stack of a solid oxide fuel cell, the method for measuring the electrical characteristics of a fuel cell has a first resistance value R 1 with respect to an arbitrary single cell 201 at room temperature when the fuel cell 200 is not generating power. A charging curve recording step of recording a time change of the charging voltage value of the single cell 201 as a charging curve C1 by connecting the external resistor 12 and the constant voltage DC power supply 11 to form the charging circuit A1, The internal resistance for calculating the internal resistance value R i of the single cell 201 based on the resistance value R 1 , the DC voltage value V 0 applied by the constant voltage DC power supply 11 and the full charge voltage value V S obtained from the charging curve C 1. A capacitance value calculating step of calculating a capacitance value C i of the single cell 201 based on the time constant τ i of the single cell 201 obtained from the charge curve C1 and the internal resistance value R i. ,including. For this reason, before operating the fuel cell unit, the internal resistance value R i and the capacitance value C i of the single cell 201 can be measured accurately and in a short time over the entire cell stack.

また、燃料電池セルスタックの診断方法は、上記燃料電池セルの電気特性測定方法に従って、セルスタックの単セル２０１ごとに内部抵抗値Ｒｉ及び静電容量値Ｃｉを測定する電気特性測定工程と、単セル２０１ごとの内部抵抗値Ｒｉどうし、及び／又は、静電容量値Ｃｉどうしを比較し、セルスタックが特性の異なる単セル２０１を含むか否かを判別する異特性セル判別工程と、を含む。このため、燃料電池ユニットを作動させる前に、単セル２０１ごとの内部抵抗値Ｒｉ及び／又は静電容量値Ｃｉに基づいて、セルスタックの健全性評価を行うことができる。 Further, the diagnostic method of the fuel cell stack in accordance with the electrical characteristic measuring method of the fuel cell, and the electrical characteristic measuring step for measuring the internal resistance R i and capacitance values C i for each single cell 201 of the cell stack The different characteristic cell discrimination step of comparing the internal resistance values R i and / or the capacitance values C i of the single cells 201 to determine whether the cell stack includes the single cells 201 having different characteristics. And including. Therefore, before operating the fuel cell unit, based on the internal resistance R i and / or the capacitance value C i of each unit cell 201, integrity evaluation of the cell stack can be performed.

次に、本発明の第２実施形態に係る燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法について説明する。先ず、燃料電池セルの電気特性測定方法で用いられる電気特性測定装置１の回路の構成について再び図１を参照しながら説明する。図１は、単セル２０１の充電用回路を形成した状態を示す回路図である。   Next, a method for measuring electric characteristics of a fuel cell and a method for diagnosing a fuel cell stack according to a second embodiment of the present invention will be described. First, the configuration of the circuit of the electrical property measuring apparatus 1 used in the electrical property measuring method for fuel cells will be described with reference to FIG. 1 again. FIG. 1 is a circuit diagram showing a state where a charging circuit for a single cell 201 is formed.

図１に示すように、第２実施形態における電気特性測定装置１は、第１実施形態で使用したものと基本的に同じ構成を有しているが、定電圧直流電源１１の接続を遮断して放電用回路Ａ２（符号省略）を形成可能になっている点が相違している。放電用回路Ａ２は、図１において、定電圧直流電源１１と第１外部抵抗１２の間の電気接続を切断、第１外部抵抗１２と単セル２０１の間の電気接続を切断、又は単セル２０１と定電圧直流電源１１との間の電気接続を切断することにより実行される。なお、実用的な回路設計においては、予め電気特性測定装置１の所要の箇所にスイッチを介在させておき、このスイッチを操作することにより充電用回路Ａ１と放電用回路Ａ２の切り換えを行えばよい。   As shown in FIG. 1, the electrical characteristic measuring apparatus 1 in the second embodiment has basically the same configuration as that used in the first embodiment, but the connection of the constant voltage DC power supply 11 is cut off. The difference is that the discharge circuit A2 (reference numeral omitted) can be formed. In FIG. 1, the discharging circuit A2 disconnects the electrical connection between the constant voltage DC power supply 11 and the first external resistor 12, disconnects the electrical connection between the first external resistor 12 and the single cell 201, or the single cell 201. And the constant voltage DC power source 11 are cut off. In practical circuit design, a switch is interposed in advance in a required portion of the electrical characteristic measuring apparatus 1, and the charging circuit A1 and the discharging circuit A2 are switched by operating this switch. .

次に、燃料電池セルの電気特性測定方法について図３を参照しながら説明する。図３は、単セル２０１充電曲線及び放電曲線（すなわち、充放電曲線）である。第２実施形態に係る燃料電池セルの電気特性測定方法は、充放電曲線記録工程と、内部抵抗値算出工程と、静電容量値算出工程と、を含んでいる。   Next, a method for measuring the electrical characteristics of the fuel cell will be described with reference to FIG. FIG. 3 shows a single cell 201 charging curve and discharging curve (that is, a charging / discharging curve). The method for measuring the electrical characteristics of a fuel cell according to the second embodiment includes a charge / discharge curve recording step, an internal resistance value calculating step, and a capacitance value calculating step.

充放電曲線記録工程では、燃料電池２００が発電を行っていない常温下で、任意の単セル２０１に対して、第１外部抵抗１２及び定電圧直流電源１１を接続して充電用回路Ａ１を形成することにより、単セル２０１の充電電圧値の時間変化を充電曲線Ｃ２として記録した後、定電圧直流電源１１の接続を遮断して放電用回路Ａ２を形成することにより、単セルの充電電圧値の時間変化を放電曲線Ｃ３として記録する。   In the charge / discharge curve recording step, the charging circuit A1 is formed by connecting the first external resistor 12 and the constant voltage DC power source 11 to an arbitrary unit cell 201 at room temperature where the fuel cell 200 is not generating power. Thus, after the time change of the charging voltage value of the single cell 201 is recorded as the charging curve C2, the connection of the constant voltage DC power source 11 is cut off to form the discharging circuit A2, thereby forming the charging voltage value of the single cell. Is recorded as a discharge curve C3.

具体的には、充放電曲線記録工程では、先ず、燃料電池２００が燃料電池ユニットに搭載されていない状態（典型的には、組立・焼成・還元処理済みセルスタックが出荷前の状態）で、測定対象単セル２０１に対して、上述した電気特性測定装置１を接続する。そして、測定対象単セル２０１に所定の直流電圧値Ｖ０を印加して充電を開始する。単セル２０１の充電中は、電圧計１３により充電曲線Ｃ２を記録し、充電電圧値が飽和した時点で満充電電圧値ＶＳに達したものと判断して充電操作を終了する。 Specifically, in the charge / discharge curve recording step, first, in a state where the fuel cell 200 is not mounted on the fuel cell unit (typically, the assembled / fired / reduced cell stack is in a state before shipment), The above-described electrical property measuring apparatus 1 is connected to the measurement target single cell 201. Then, a predetermined DC voltage value V 0 is applied to the measurement target single cell 201 to start charging. During charging of the single cell 201, the charging curve C2 is recorded by the voltmeter 13, and when the charging voltage value is saturated, it is determined that the full charging voltage value V S has been reached, and the charging operation is terminated.

次に、測定対象単セル２０１に直流電圧値Ｖ０が印加されないように電圧印加を遮断し、放電を開始する。単セル２０１の放電中は、電圧計１３により放電曲線Ｃ３を記録し、充電電圧値が満充電電圧値ＶＳの３６．８％相当の値に達した時点以降で放電操作を終了する。 Next, voltage application is interrupted so that the DC voltage value V 0 is not applied to the measurement target single cell 201, and discharge is started. During the discharge of the unit cells 201, a discharge curve C3 recorded by the voltmeter 13, to end the discharge operation at the subsequent time point when the charge voltage value reached 36.8% equivalent value of the full charge voltage value V S.

充放電曲線記録工程に続く内部抵抗値算出工程では、第１抵抗値Ｒ１、定電圧直流電源１１により印加した直流電圧値Ｖ０、及び充電曲線Ｃ２より求めた測定対象単セル２０１の満充電電圧値ＶＳに基づいて、測定対象単セル２０１の内部抵抗値Ｒｉを算出する。具体的には、上述した式（１）を使用して内部抵抗値Ｒｉを求める。 In the internal resistance value calculation step subsequent to the charge / discharge curve recording step, the full charge of the measurement target single cell 201 obtained from the first resistance value R 1 , the DC voltage value V 0 applied by the constant voltage DC power source 11, and the charge curve C 2. Based on the voltage value V S , the internal resistance value R i of the measurement target single cell 201 is calculated. Specifically, the internal resistance value R i is obtained using the above-described equation (1).

内部抵抗値算出工程に続く静電容量値算出工程では、放電曲線Ｃ３より求めた測定対象単セル２０１の時定数τｉ、及び内部抵抗値Ｒｉに基づいて、測定対象単セル２０１の静電容量値Ｃｉを求める。具体的には、上述した式（２）を使用して静電容量値Ｃｉを求める。 In the capacitance value calculation step subsequent to the internal resistance value calculation step, the electrostatic capacitance of the measurement target single cell 201 is determined based on the time constant τ i of the measurement target single cell 201 obtained from the discharge curve C3 and the internal resistance value R i. The capacitance value C i is obtained. Specifically, the capacitance value C i is obtained using the above-described equation (2).

ここで、単セル２０１の時定数τｉは、放電開始時点の充電電圧値（すなわち、満充電電圧値ＶＳ）を１００％として、放電中の充電電圧値が満充電電圧値ＶＳの３６．８％（＝１／ｅ×１００）まで低下するのに要する時間である。図３の放電曲線Ｃ３に示すように、放電開始時刻をｔ１とし、充電電圧値がＶＳ×１／ｅとなった時刻をｔ２とすると、単セル２０１の時定数τｉは、次の式（４）で表わされる。
τｉ＝ｔ２−ｔ１ … （４） Here, the time constant τ i of the single cell 201 is such that the charge voltage value at the start of discharge (that is, the full charge voltage value V S ) is 100%, and the charge voltage value during discharge is 36 of the full charge voltage value V S. This is the time required to decrease to 8% (= 1 / e × 100). As shown in the discharge curve C3 in FIG. 3, the discharge start time and t 1, when the time at which the charging voltage value becomes V S × 1 / e and t 2, constant tau i time of the single cell 201, the following (4).
τ i = t 2 −t 1 (4)

次に、第２実施形態に係る燃料電池セルスタックの診断方法は、上述した燃料電池セルの電気特性測定方法に従う電気特性測定工程と、異特性セル判別工程と、を含んでいる。電気特性測定工程では、内部抵抗値算出工程で求めた内部抵抗値Ｒｉ及び静電容量値算出工程で求めた静電容量値Ｃｉを取得し、単セルの異質性を判別するための情報として利用する。なお、異特性セル判別工程の内容は、第１実施形態と同じであるので、詳細な説明を省略する。 Next, the method for diagnosing a fuel cell stack according to the second embodiment includes an electrical property measurement step according to the above-described electrical property measurement method for a fuel cell, and a different property cell discrimination step. In the electrical characteristic measurement process, information for acquiring the internal resistance value R i obtained in the internal resistance value calculation process and the capacitance value C i obtained in the capacitance value calculation process and determining the heterogeneity of the single cell. Use as Since the contents of the different characteristic cell discrimination step are the same as those in the first embodiment, detailed description thereof is omitted.

第２実施形態に係る燃料電池セルの電気特性測定方法、及び燃料電池セルスタックの診断方法によれば、以下のような効果を得ることができる。   According to the fuel cell electrical characteristics measurement method and fuel cell stack diagnostic method according to the second embodiment, the following effects can be obtained.

燃料電池セルの電気特性測定方法では、固体酸化型燃料電池のセルスタックにおいて、燃料電池２００が発電を行っていない常温下で、任意の単セル２０１に対して第１抵抗値Ｒ１を有する第１外部抵抗１２、及び定電圧直流電源１１を接続して充電用回路Ａ１を形成することにより、単セル２０１の充電電圧値の時間変化を充電曲線Ｃ２として記録した後、定電圧直流電源１１の接続を遮断して放電用回路Ａ２を形成することにより、単セル２０１の充電電圧値の時間変化を放電曲線Ｃ３として記録する充放電曲線記録工程と、第１抵抗値Ｒ１、定電圧直流電源１１により印加した直流電圧値Ｖ０、及び充電曲線Ｃ２より求めた満充電電圧値ＶＳに基づいて、単セル２０１の内部抵抗値Ｖｉを算出する内部抵抗値算出工程と、放電曲線Ｃ３より求めた単セル２０１の時定数τｉ、及び内部抵抗値Ｒｉに基づいて、単セル２０１の静電容量値Ｃｉを算出する静電容量値算出工程と、を含む。このため、燃料電池ユニットを作動させる前に、セルスタックの全体に亘って単セル２０１の内部抵抗値Ｒｉ及び静電容量値Ｃｉを正確且つ短時間で計測ことができる。 In the method for measuring the electrical characteristics of a fuel cell, the first resistance value R 1 of an arbitrary single cell 201 in a cell stack of a solid oxide fuel cell has a first resistance value R 1 at room temperature when the fuel cell 200 is not generating power. 1 By connecting the external resistor 12 and the constant voltage DC power source 11 to form the charging circuit A1, the time change of the charging voltage value of the single cell 201 is recorded as the charging curve C2, and then the constant voltage DC power source 11 By disconnecting the connection and forming the discharge circuit A2, the charge / discharge curve recording step of recording the time change of the charge voltage value of the single cell 201 as the discharge curve C3, the first resistance value R 1 , the constant voltage DC power supply DC voltage value V 0 which is applied by 11, and based on the full charge voltage value V S determined from the charging curve C2, and the internal resistance value calculation step of calculating an internal resistance value V i of the unit cell 201, discharge curve A capacitance value calculating step of calculating the capacitance value C i of the single cell 201 based on the time constant τ i of the single cell 201 and the internal resistance value R i obtained from C3. For this reason, before operating the fuel cell unit, the internal resistance value R i and the capacitance value C i of the single cell 201 can be measured accurately and in a short time over the entire cell stack.

また、燃料電池セルスタックの診断方法は、上記燃料電池セルの電気特性測定方法に従って、セルスタックの単セル２０１ごとに内部抵抗値Ｒｉ及び静電容量値Ｃｉを測定する電気特性測定工程と、単セル２０１ごとの内部抵抗値Ｒｉどうし、及び／又は、静電容量値Ｃｉどうしを比較し、セルスタックが特性の異なる単セル２０１を含むか否かを判別する異特性セル判別工程と、を含む。このため、燃料電池ユニットを作動させる前に、単セル２０１ごとの内部抵抗値Ｒｉ及び／又は静電容量値Ｃｉに基づいて、セルスタックの健全性評価を行うことができる。 Further, the diagnostic method of the fuel cell stack in accordance with the electrical characteristic measuring method of the fuel cell, and the electrical characteristic measuring step for measuring the internal resistance R i and capacitance values C i for each single cell 201 of the cell stack The different characteristic cell discrimination step of comparing the internal resistance values R i and / or the capacitance values C i of the single cells 201 to determine whether the cell stack includes the single cells 201 having different characteristics. And including. Therefore, before operating the fuel cell unit, based on the internal resistance R i and / or the capacitance value C i of each unit cell 201, integrity evaluation of the cell stack can be performed.

本発明は、上記実施形態に限定されることはなく、特許請求の範囲に記載された技術的範囲において変形が可能である。例えば、上記実施形態では、異特性セル判別工程は、単セル２０１ごとの内部抵抗値Ｒｉどうし、及び、静電容量値Ｃｉどうしを比較し、セルスタックが特性の異なる単セル２０１を含むか否かを判別したが、これに限定されない。異特性セル判別工程は、各単セル２０１の内部抵抗値Ｒｉのみを比較することにより、その異質性を判別してもよいし、各単セル２０１の静電容量値Ｃｉのみを比較することにより、その異質性を判別してもよい。 The present invention is not limited to the above embodiment, and can be modified within the technical scope described in the claims. For example, in the above embodiment, the different characteristic cell determination process, and if the internal resistance Ri of each unit cell 201, and compares the with the same capacitive value C i, including single cells 201 cell stack different characteristics Although it was determined whether or not, it is not limited to this. In the different characteristic cell discrimination step, the heterogeneity may be discriminated by comparing only the internal resistance value Ri of each single cell 201, or only the capacitance value C i of each single cell 201 is compared. Thus, the heterogeneity may be determined.

また、上記実施形態では、燃料電池２００が燃料電池ユニットに搭載されていない状態で、測定対象単セル２０１の電気特性を測定するケースを例示した。しかし、燃料電池２００が発電を行っていない常温下であれば、燃料電池２００が燃料電池ユニットに搭載されている状態で、測定対象単セル２０１の電気特性を測定してもよい。   Moreover, in the said embodiment, the case where the electrical property of the measurement object single cell 201 was measured in the state in which the fuel cell 200 is not mounted in the fuel cell unit was illustrated. However, if the fuel cell 200 is at a room temperature where power generation is not performed, the electrical characteristics of the measurement target single cell 201 may be measured in a state where the fuel cell 200 is mounted on the fuel cell unit.

１１ 定電圧直流電源
１２ 第１外部抵抗
２００ 燃料電池
２０１ 単セル
Ａ１ 充電用回路
Ａ２ 放電用回路
Ｃ１、Ｃ２ 充電曲線
Ｃ３ 放電曲線 11 constant voltage DC power source 12 first external resistance 200 fuel cell 201 single cell A1 charging circuit A2 discharging circuit C1, C2 charging curve C3 discharging curve

Claims (3)

固体酸化型燃料電池のセルスタックにおいて、前記燃料電池が発電を行っていない常温下で、任意の単セルに対して第１抵抗値を有する第１外部抵抗、及び定電圧直流電源を接続して充電用回路を形成することにより、前記単セルの充電電圧値の時間変化を充電曲線として記録する充電曲線記録工程と、
前記第１抵抗値、前記定電圧直流電源より印加した直流電圧値、及び前記充電曲線より求めた前記単セルの満充電電圧値に基づいて、前記単セルの内部抵抗値を算出する内部抵抗値算出工程と、
前記充電曲線より求めた前記単セルの時定数、及び前記内部抵抗値に基づいて、前記単セルの静電容量値を算出する静電容量値算出工程と、を含む
燃料電池セルの電気特性測定方法。 In a cell stack of a solid oxide fuel cell, a first external resistor having a first resistance value and a constant voltage DC power source are connected to an arbitrary single cell at room temperature where the fuel cell is not generating power. A charging curve recording step of recording a time change of the charging voltage value of the single cell as a charging curve by forming a charging circuit;
An internal resistance value for calculating an internal resistance value of the single cell based on the first resistance value, a DC voltage value applied from the constant voltage DC power source, and a full charge voltage value of the single cell obtained from the charging curve. A calculation process;
A capacitance value calculating step of calculating a capacitance value of the single cell based on the time constant of the single cell obtained from the charging curve and the internal resistance value, and measuring electric characteristics of the fuel cell. Method. 固体酸化型燃料電池のセルスタックにおいて、前記燃料電池が発電を行っていない常温下で、任意の単セルに対して第１抵抗値を有する第１外部抵抗、及び定電圧直流電源を接続して充電用回路を形成することにより、前記単セルの充電電圧値の時間変化を充電曲線として記録した後、前記定電圧直流電源の接続を遮断して放電用回路を形成することにより、前記単セルの充電電圧値の時間変化を放電曲線として記録する充放電曲線記録工程と、
前記第１抵抗値、前記定電圧直流電源により印加した直流電圧値、及び前記充電曲線より求めた前記単セルの満充電電圧値に基づいて、前記単セルの内部抵抗値を算出する内部抵抗値算出工程と、
前記放電曲線より求めた前記単セルの時定数、及び前記内部抵抗値に基づいて、前記単セルの静電容量値を算出する静電容量値算出工程と、を含む
燃料電池セルの電気特性測定方法。 In a cell stack of a solid oxide fuel cell, a first external resistor having a first resistance value and a constant voltage DC power source are connected to an arbitrary single cell at room temperature where the fuel cell is not generating power. By forming a charging circuit, the time change of the charging voltage value of the single cell is recorded as a charging curve, and then disconnecting the constant voltage DC power source to form a discharging circuit. A charge / discharge curve recording step of recording the time change of the charging voltage value as a discharge curve;
An internal resistance value for calculating an internal resistance value of the single cell based on the first resistance value, a DC voltage value applied by the constant voltage DC power source, and a full charge voltage value of the single cell obtained from the charging curve. A calculation process;
A capacitance value calculating step of calculating a capacitance value of the single cell based on the time constant of the single cell obtained from the discharge curve and the internal resistance value, and measuring electric characteristics of the fuel cell. Method. 請求項１又は請求項２に記載の方法に従って、前記セルスタックの単セルごとに前記内部抵抗値及び前記静電容量値を測定する電気特性測定工程と、
前記単セルごとの前記内部抵抗値どうし、及び／又は、前記静電容量値どうしを比較し、前記セルスタックが特性の異なる前記単セルを含むか否かを判別する異特性セル判別工程と、を含む
燃料電池セルスタックの診断方法。 According to the method of claim 1 or claim 2, an electrical property measurement step of measuring the internal resistance value and the capacitance value for each single cell of the cell stack;
A different characteristic cell determination step of comparing the internal resistance values for each single cell and / or the capacitance values, and determining whether the cell stack includes the single cells having different characteristics; A method for diagnosing a fuel cell stack including
JP2016043774A 2016-03-07 2016-03-07 Method for measuring electrical characteristics of fuel battery cell, and method for diagnosing fuel battery cell stack Pending JP2017162573A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114325394A (en) * 2021-12-29 2022-04-12 上海电气国轩新能源科技有限公司 Method, system, device and medium for estimating SOC of battery stack
CN115754825A (en) * 2022-11-08 2023-03-07 中山市新益昌自动化设备有限公司 Capacitance detection method and device and data board

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114325394A (en) * 2021-12-29 2022-04-12 上海电气国轩新能源科技有限公司 Method, system, device and medium for estimating SOC of battery stack
CN114325394B (en) * 2021-12-29 2024-05-14 上海电气国轩新能源科技有限公司 Method, system, equipment and medium for estimating battery stack SOC
CN115754825A (en) * 2022-11-08 2023-03-07 中山市新益昌自动化设备有限公司 Capacitance detection method and device and data board

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