WO2007110970A1 - Procede de calcul de la resistance d'interface - Google Patents

Procede de calcul de la resistance d'interface Download PDF

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Publication number
WO2007110970A1
WO2007110970A1 PCT/JP2006/307161 JP2006307161W WO2007110970A1 WO 2007110970 A1 WO2007110970 A1 WO 2007110970A1 JP 2006307161 W JP2006307161 W JP 2006307161W WO 2007110970 A1 WO2007110970 A1 WO 2007110970A1
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WIPO (PCT)
Prior art keywords
electrode side
resistance
frequency
fuel cell
call
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PCT/JP2006/307161
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English (en)
Japanese (ja)
Inventor
Hideo Michibata
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The Tokyo Electric Power Company, Incorporated
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Publication date
Application filed by The Tokyo Electric Power Company, Incorporated filed Critical The Tokyo Electric Power Company, Incorporated
Priority to JP2008507352A priority Critical patent/JP5007963B2/ja
Priority to PCT/JP2006/307161 priority patent/WO2007110970A1/fr
Publication of WO2007110970A1 publication Critical patent/WO2007110970A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04634—Other electric variables, e.g. resistance or impedance
    • H01M8/04641—Other electric variables, e.g. resistance or impedance of the individual fuel cell
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention is a method for measuring the interface resistance at the time of operation of a fuel cell, specifically, calculating the interface resistance at the interface between the fuel electrode and the electrolyte and the interface resistance at the interface between the air electrode and the electrolyte. Regarding the method. Background art
  • the fuel cell has a fuel cell unit configured such that an electrolyte is sandwiched between a fuel electrode and an air electrode.
  • the fuel cell will be described with reference to FIG. Fig. 1'4 is a schematic diagram showing a fuel cell.
  • the fuel cell 4 4 is formed so that the electrolyte 4 1 is sandwiched between the fuel electrode 4 2 and the air electrode 4 3.
  • the resistance at the time of operation of the fuel cell 44 is mainly the ohmic resistance of the electrolyte 41 itself, the ohmic resistance of the fuel electrode 42 itself, the ohmic resistance of the air electrode 43 itself, The sum of the interface resistance at the interface between the fuel electrode 4 2 and the electrolyte 4 1 at the time and the interface resistance at the interface between the air electrode 4 3 and the electrolyte 4 1 during operation.
  • the total of the ohmic resistance of the electrolyte 41 itself, the ohmic resistance of the fuel electrode 42 itself, and the ohmic resistance of the air electrode 43 itself is also referred to as the ohmic resistance Rb of the cell.
  • the interface resistance at the electrode-electrolyte interface is also described as the fuel electrode-side interface resistance Ria, and the interface resistance at the air electrode-electrolyte interface is also described as the air electrode-side interface resistance Ric.
  • the ohmic resistance of the fuel electrode 42 itself is applied to the electrolyte 41. It is obtained by measuring the resistance of the fuel electrode 42 before being bonded, or by preparing the fuel electrode 42 not bonded to the electrolyte 41 and measuring its resistance. . The same applies to the ohmic resistance of the electrolyte 41 itself and the ohmic resistance of the air electrode 43 itself.
  • the fuel electrode side interface resistance R ia and the air electrode side interface resistance R ic are resistances at the interface between the fuel electrode 42 or the air electrode 43 and the electrolyte 41, so The resistance cannot be measured unless the electrode 4 2 or the air electrode 4 3 is joined to the electrolyte 4 1.
  • FIG. 15 is a schematic diagram showing a conventional method for measuring interface resistance, and is a schematic diagram of a cross section of a cell for a fuel cell at the time of measuring interface resistance.
  • the fuel cell 4 4 a is formed by sandwiching the electrolyte 4 1 a between the fuel electrode 4 2 a and the air electrode 4 3 a, and The reference electrode 5 1 is provided at the intermediate potential point 5 5 a.
  • the position where the reference electrode 51 is installed is the side surface of the electrolyte 41a, and the middle point in the thickness direction of the electrolyte 41a.
  • the resistance between the fuel electrode terminal 53 and the reference electrode 51 and the resistance between the reference electrode 51 and the air electrode terminal 54 under the same operating conditions as the fuel cell 44a. Measure the resistance of each.
  • the fuel electrode side interface resistance R ia resistance 5 3 — 5 1 — (R ba + O. 5 R bs) (5)
  • resistance 5 3 _ 5 1 represents the resistance between the fuel electrode terminal 5 3 and the reference electrode 51
  • R ba represents the ohmic resistance of the fuel electrode 4 2 a
  • R bs Represents the ohmic resistance of the electrolyte 41a.
  • Air electrode side interface resistance R ic Resistance 5 i— 5 4 — (R bc + 0.5 R bs) (6)
  • resistance 5 1 — 5 4 represents the resistance between the reference electrode 5 1 and the negative electrode terminal 5 4
  • R bc represents the ohmic resistance of the air electrode 4 3 a
  • R bs represents the ohmic resistance of the electrolyte 4 1 a.
  • the intermediate potential point 55a refers to a point that bisects the ohmic resistance of the electrolyte 41a.
  • the reference electrode can be installed without any problem as long as the thickness of the electrolyte is sufficient.
  • the thickness of the electrolyte of the fuel cell currently in practical use is extremely thin, about 5 to 100 ⁇ m, the reference electrode is used as the electrolyte of the fuel cell currently in practical use. It was difficult to install. In other words, there is a problem that the interface resistance cannot be calculated in the case of fuel cell cells that are currently in practical use.
  • the area and shape of the junction between the electrolyte 4 1 a and the fuel electrode 4 2 a are the same as those of the electrolyte 4 1 a and the air electrode. Since the area and shape of the junction with 4 3 a are the same, the potential change in the electrolyte 4 1 a is subject to up and down. That is, when the equipotential line 5 2 a in the electrolyte 4 1 a is shown, in the case of the fuel cell 4 4 a, the equipotential line 5 2 a is connected to the fuel electrode 4 2 a and the air electrode 4. 3 From a, spread in the shape of the top and bottom objects. Therefore, in the fuel cell 4 4 a, the intermediate potential point 55 a appears on the side surface of the electrolyte 41 a and is the intermediate point in the thickness direction of the electrolyte 41 a.
  • Fig. 16 shows a fuel cell in which the area or shape of the junction between the electrolyte and the fuel electrode is not the same as the area or shape of the junction between the electrolyte and the air electrode It is typical sectional drawing.
  • the area and shape of the junction between the electrolyte 4 1 b and the fuel electrode 4 2 b are the same as the junction between the electrolyte 4 1 b and the air electrode 4 3 b. It is not the same as the area and shape of the part.
  • the equipotential line 5 2 b extends from the fuel electrode 4 2 b and the air electrode 4 3 b in a shape that is not vertically aligned.
  • the intermediate potential point 55b does not appear on the side surface of the electrolyte 41b, but appears on the surface 56 where the fuel electrode 42b is joined, and
  • the position where the intermediate potential point 5 5 b appears varies depending on the area or shape of the junction. Therefore, in the case of the fuel cell 4 4 b, the reference electrode cannot be installed at an accurate position. There was a problem that accurate interface resistance could not be measured.
  • the problem of the present invention is that even if the thickness of the electrolyte of the fuel cell cell is small, or the area or shape of the junction between the electrolyte and the fuel electrode is the same as the area or shape of the junction between the electrolyte and the air electrode.
  • An object of the present invention is to provide an interface resistance calculation method that can calculate the interface resistance even if they are not the same. Disclosure of the invention
  • the present invention (1) is an interface resistance calculation method for calculating a fuel electrode side interface resistance R ia and an air electrode side interface resistance R ic during operation of a calculation target fuel cell.
  • the complex impedance measurement of the calculation target fuel cell is performed under the first measurement condition and the second measurement condition that are different only in the gas composition of the fuel electrode side gas, and then the real number when the frequency in the first measurement condition is n Difference between the resistance value R 1 rn and the real resistance value R 2 rn when the frequency in the second measurement condition is n (1-2) rn in the following formula (1):
  • the complex impedance measurement of the calculation target fuel cell is performed under the third measurement condition and the fourth measurement condition, which differ only in the gas composition of the air electrode side gas, and then the frequency in the third measurement condition is n
  • the difference between the real part resistance value R 3 rn and the real part resistance value R 4 rn when the frequency in the fourth measurement condition is n ⁇ R (3 -4) rn is expressed by the following equation (2):
  • R i c R r c (ma x) — R r c (m i n) (4)
  • an interface resistance calculation step for obtaining an air electrode side interface resistance R ic, and a method for calculating the interface resistance comprising: Further, the present invention (2) is a method for calculating the interface resistance for calculating the fuel electrode side interface resistance R ia and the air electrode side interface resistance R ic during operation of the calculation target fuel cell.
  • the complex impedance measurement of the calculation target fuel cell is performed under the first measurement condition and the second measurement condition that are different only in the gas composition of the fuel electrode side gas, and then the real number when the frequency in the first measurement condition is n
  • the difference between the part resistance value R 1 rn and the real part resistance value R 2 rn when the frequency in the second measurement condition is n is R (1 ⁇ 2) rn as the following formula (1):
  • An equivalent circuit having (i) a first resistor connected in series; (ii) a second resistor and a first capacitor connected in parallel; and (iii) a third resistor and a second capacitor connected in parallel.
  • Fig. 1 is a schematic diagram of the call-call plot of the fuel cell for calculation consisting of two arcs.
  • Fig. 2 shows the calculation consisting of three arcs. It is a schematic diagram of the Cole-Cole-plot of the target fuel cell.
  • FIG. 3 is a schematic diagram of the call-call plot of the fuel cell for calculation when complex impedance is measured under the first measurement condition and the second measurement condition
  • Fig. 4 is a real number.
  • Part resistance difference first graph 14 and real part resistance difference second graph 1 4 1 is a schematic diagram
  • FIG. 5 is a complex impedance measurement under the third measurement condition and the fourth measurement condition
  • FIG. 6 is a diagram showing an equivalent circuit 21
  • FIG. 7 is a diagram showing an equivalent circuit 30.
  • FIG. Fig. 8 shows the call 1 plot for measurement 1
  • Fig. 9 shows the call call for measurement 2.
  • Fig. 10 shows the plot for call 2.
  • Fig. 10 shows the call for measurement 3.
  • Figure 1 shows the Cole 'plot
  • Figure 1 shows the Cole Cole plot for measurement 4.
  • FIG. 14 is a schematic diagram showing a fuel cell
  • Fig. 15 is a schematic diagram showing a conventional interface resistance measurement method
  • Yes Fig. 16 is a schematic diagram showing a fuel cell, where the area or shape of the junction between the electrolyte and the fuel electrode is not the same as the area or shape of the junction between the electrolyte and the air electrode.
  • the method for measuring the interface resistance according to the first aspect of the present invention is a method for calculating the interface resistance by calculating the fuel electrode side interface resistance R ia and the air electrode side interface resistance R ic when the fuel cell for calculation is operated. Because
  • the complex impedance measurement of the calculation target fuel cell is performed under the first measurement condition and the second measurement condition that are different only in the gas composition of the fuel electrode side gas, and then the real part when the frequency in the first measurement condition is n
  • the difference between the resistance value R 1 rn and the real part resistance value R 2 rn when the frequency in the second measurement condition is n (R (1 ⁇ 2) rn is expressed by the following equation (1):
  • the complex impedance measurement of the calculation target fuel cell is performed under the third measurement condition and the fourth measurement condition that are different only in the gas composition of the air electrode side gas, and then the frequency in the third measurement condition is n.
  • the difference between the real part resistance R 3 rn at the time and the real part resistance R 4 rn when the frequency in the fourth measurement condition is n ⁇ R (3-4) rn is expressed by the following equation (2):
  • R ia R ra max) — R ra (min) (3) is calculated to obtain the fuel electrode side interface resistance R ia, and then the calculation target fuel cell cell obtained in the first step is calculated.
  • the maximum value R rc (max) of the real part resistance value and the minimum value R rc of the real part resistance value of the arc identified as the arc originating from the air electrode side interface in the third step The difference from (min) is the following formula (4):
  • R i c R r c (max) ⁇ R r c (m i n) (4) to obtain the air electrode side interface resistance R i c, and a method for calculating the interface resistance.
  • the calculation target fuel cell for the interface resistance calculation method is a fuel cell for which the interface resistance is calculated.
  • the complex impedance of the calculated fuel cell is measured under the operating condition for calculating the interface resistance.
  • the operating condition for calculating the interface resistance is a specific operating condition for which the interface resistance is desired to be calculated. That is, in the first step, first, the complex impedance measurement of the calculation target fuel cell is performed under a specific operating condition for which calculation of the interface resistance is desired.
  • the operating conditions for calculating the interface resistance are the fuel concentration of the fuel electrode side gas, the oxygen concentration of the air electrode side gas, the operating temperature of the cell, the water vapor concentration of the fuel electrode side gas, the water vapor concentration of the air electrode side gas, etc. Consists of various elements.
  • the operating conditions for calculating the interface resistance always include three elements: the gas composition of the fuel electrode side gas, the gas composition of the air electrode side gas, and the operating temperature of the cell.
  • the calculation target fuel cell includes an electrolyte sandwiched between a fuel electrode and an air electrode.
  • a solid oxide fuel cell a phosphoric acid fuel cell, a molten carbonate fuel cell, solid A polymer fuel cell is exemplified.
  • the complex impedance measurement means that when a voltage is applied by applying a slight voltage AC component of 100 mV or less between the fuel electrode and the air electrode of the calculation target fuel cell, the AC component It is to measure the current and its phase difference when the frequency is changed from about 100 kHz to about 1 MHz.
  • the method for performing the complex impedance measurement is not particularly limited as long as it is a complex impedance measurement method that is usually used for grasping the characteristics of the fuel cell.
  • the complex impedance measurement is also called AC impedance measurement.
  • the complex impedance measurement according to the second step and the complex impedance measurement according to the third step described later are the same as the complex impedance measurement according to the first step.
  • FIG. 2 is a call of the cell for calculation target fuel cell consisting of three arcs.
  • ⁇ Schematic diagram of call 'plot The call cell plot for the calculation target fuel cell obtained in the first step is the simplest of the two plots, as shown in Fig. 1.
  • Cole ⁇ call 'plot 1 a consisting of 2 a and second arc 3 a.
  • there are three arcs that is, the first arc 2 as shown in FIG. b, a call consisting of the second arc 3 b and the third arc 4. Coll.
  • the first arc is counted from the side where the real part resistance value is small in the arc of the Cole-Cole 'plot of the calculation target fuel cell obtained in the first step, This refers to the first arc
  • the second arc is counted from the side with the smaller real part resistance value in the arc of the Cole Cole plot of the fuel cell to be calculated obtained in the first step.
  • One of the first arc and the second arc is an arc derived from the fuel electrode side interface, and the other is an arc derived from the air electrode side interface.
  • the Cole-Cole-Plot curve of the calculation target fuel cell obtained by actually performing the complex impedance measurement rarely has the same shape as a perfect circular arc.
  • the wording of arc is used.
  • the complex impedance measurement of the calculation target fuel cell is performed under the first measurement condition and the second measurement condition that are different only in the gas composition of the fuel electrode side gas.
  • the complex impedance measurement of the calculation target fuel cell is performed under the first measurement condition and the second measurement condition that are different only in the gas composition of the fuel electrode side gas. It means that the complex impedance measurement of the cell for the fuel cell to be calculated is performed under two measurement conditions in which only the gas composition of the fuel electrode side gas is fixed and only the gas composition of the fuel electrode side gas is changed. Specifically, for example, the hydrogen concentration of the fuel electrode side gas in the first measurement condition is set to 100 volume%, and the hydrogen concentration of the fuel electrode side gas in the second measurement condition is set to 10 volumes. / 0, and for the elements constituting the other measurement conditions, none of the first measurement condition and said second measurement conditions were the same, the complex Inpi of the calculated output target fuel cell - performing dance measurement.
  • the measurement conditions related to the first measurement condition and the second measurement condition are as follows: fuel concentration in the fuel electrode side gas, oxygen concentration in the air electrode side gas, cell operating temperature, water vapor concentration in the fuel electrode side gas, air electrode It consists of various factors such as the water vapor concentration of the side gas.
  • the measurement conditions always include three elements: the gas composition of the fuel electrode side gas, the gas composition of the air electrode side gas, and the operating temperature of the cell.
  • FIG. 3 shows a schematic diagram of a call / call plot of the cell for the calculation target fuel cell under the first measurement condition or the second measurement condition.
  • FIG. 3 shows the calculation target fuel cell in which the number of arcs of the call / call plot of the calculation target fuel cell obtained by performing the first step is two.
  • the cell of the cell to be calculated is called a Cole plot
  • the first measurement condition The call / call 'plot 1 1 of the calculation target fuel cell at 1 consists of a first arc 2c and a second arc 3c
  • the calculation target fuel cell for the second measurement condition Cole ⁇ Cole 'Plot 1 2 consists of a first arc 2d and a second arc 3d.
  • a point where the frequency in the Cole Cole 'plot 1 1 is 1 000 Hz is pointed E 1 and a point where the frequency in the Cole Cole' plot 1 2 is 100 OH z
  • FIG. 4 shows a schematic diagram of the first real part resistance difference graph.
  • the graph indicated by the symbol 14 is the real part resistance difference first graph 14, and the real part resistance difference first graph 14 is always compared to the other frequency ranges. (1 ⁇ .2) ⁇
  • the real part resistance difference first graph 14 always has a peak 15.
  • the frequency of the peak top 16 of the peak 15 is read from the real part resistance difference first draft 14, and the frequency obtained in the first step is obtained from the frequency value of the peak top 16.
  • the cell for the fuel cell to be calculated 'Cole certify the arc originating from the fuel electrode side interface. For example, if the peak top frequency in the first real part resistance difference graph is X, the frequency of the call / call 'plot of the calculation target fuel cell obtained in the first step is The arc including the point X is identified as the arc originating from the fuel electrode side interface.
  • the second step only the gas composition of the fuel electrode side gas is changed. Therefore, in the first graph of the real part resistance difference, the fact that the peak top exists at the frequency X means that the influence of the change on the fuel electrode side has an effect. Is the portion corresponding to the frequency region in the vicinity of frequency X in the Cole-Cole-Plot of the calculation target fuel cell, so that the calculation target fuel obtained in the first step is Call of battery cell. In the call plot, an arc including a point with a frequency X can be recognized as an arc originating from the fuel electrode side interface.
  • the fuel contained in the fuel electrode side gas is not particularly limited, and examples thereof include hydrogen and methane.
  • the complex impedance measurement of the calculation target fuel cell is performed under the third measurement condition and the fourth measurement condition that differ only in the gas composition of the air electrode side gas.
  • the complex impedance measurement of the calculation target fuel cell is performed under the third measurement condition and the fourth measurement condition, which are different only in the gas composition of the air electrode side gas, among the elements constituting the measurement condition, It means that the complex impedance measurement of the calculation target fuel cell is performed under two measurement conditions in which only the gas composition of the air electrode side gas is fixed and only the gas composition of the air electrode side gas is changed.
  • the oxygen concentration of the air electrode side gas under the third measurement condition is 100% by volume
  • the oxygen concentration of the air electrode side gas under the fourth measurement condition is 10% by volume, etc.
  • the complex impedance measurement of the calculation target fuel cell is performed with the third measurement condition and the fourth measurement condition being the same.
  • the measurement conditions related to the third measurement condition and the fourth measurement condition are as follows: fuel concentration in the fuel electrode side gas, oxygen concentration in the air electrode side gas, cell operating temperature, water vapor concentration in the fuel electrode side gas, air electrode side It consists of various elements such as the water vapor concentration of the gas.
  • the measurement conditions always include three elements: the gas composition of the fuel electrode side gas, the gas composition of the air electrode side gas, and the operating temperature of the cell.
  • FIG. 5 shows a schematic diagram of the call-call-plot of the cell for calculation target fuel cell under the third measurement condition or the fourth measurement condition.
  • FIG. 5 shows the calculation target fuel cell in which the number of arcs of the call / call plot of the calculation target fuel cell obtained by performing the first step is 2 and the third measurement condition and This is a call / call 'plot of the fuel cell to be calculated when complex impedance is measured under the fourth measurement condition, and a call / call of the cell for the fuel cell to be calculated under the third measurement condition.
  • Plot 17 consists of a first arc 2 e and a second arc 3 e, and the call cell call of the calculation target fuel cell under the fourth measurement condition 'plot 1 8 shows the first arc 2 f and second arc 3 f.
  • the point where the frequency in the Cole Cole 'plot 1 7 is 1 000 Hz is pointed G 1
  • the point in the Cole Cole' plot 1 8 is the point where the frequency is 1000 Hz.
  • G 2 the real part resistance value R 3 r of the point G 1 from the Cole-Cole plot 17. . .
  • the real part resistance value R 4 r 1000 of the point G 2 is obtained.
  • the difference (R 3 ri .. One R4 r 100.
  • the calculation of AR (3-4) rn is based on the change in AR (3-4) rn with respect to the frequency change, and the entire area of Cole Cole Plot 1 7 and Cole Cole Cole 'Plot 1 8 It is sufficient that the frequency interval is such that it can be observed over a range of intervals, and ⁇ R (3 ⁇ 4) rn corresponding to each frequency at a constant interval may be obtained, or the frequency interval may not be constant. Good.
  • FIG. 4 shows a schematic diagram of the second resistance difference second graph.
  • the graph denoted by reference numeral 141 is the real part resistance difference second graph 141, and the real part resistance difference second graph 141 is always compared to other frequency ranges.
  • the real part resistance difference second graph 1 4 1 always has a peak 1 5 1. Then, the frequency of the peak top 16 1 of the peak 1 51 is read from the second resistance difference second graph 141, and the frequency value of the peak top 1 61 1 is obtained in the first step. In addition, the arc derived from the air electrode side interface is identified in the call / call plot of the fuel cell to be calculated.
  • the frequency of the Cole-Cole 'plot of the calculation target fuel cell obtained in the first step is: An arc including a point where y is y is recognized as an arc derived from the air electrode side interface.
  • the fact that the frequency top has the peak top means that the air electrode side changes. Is the portion corresponding to the frequency region in the vicinity of the frequency y in the Cole-Cole-Plot of the calculation target fuel cell, so that the calculation target fuel obtained in the first step is In the Cole-Cole 'plot of the battery cell, the arc including the point where the frequency is y can be recognized as the arc originating from the air electrode side interface.
  • the interface resistance calculation step will be described with reference to FIG.
  • the first arc 2a of the Cole Cole plot 1a is an arc originating from the fuel electrode side interface
  • the circular arc 3a is recognized as an arc originating from the air electrode side interface.
  • the intersection of the first arc 2a and the horizontal axis that is, the point where the resistance value of the imaginary part of the first arc 2a is "0" is point A 1
  • the intersection of the first arc 2a and the second arc 3a is the point B1, the intersection of the second arc 3a and the horizontal axis, that is, the imaginary part resistance of the second arc 3a.
  • the R ra (min) is the real part resistance value of the point A 1
  • the R ra (max) is the point B 1
  • R c (min) is the real part resistance value of the point B 1
  • R rc (max) is the real part resistance value of the point C 1.
  • the call / call plot of the calculation target fuel cell obtained by performing the first step is composed of three arcs
  • the first arc 2b of the Cole-Cole 'plot 1b is an arc originating from the fuel electrode side interface
  • the second arc 3 It is assumed that b is an arc derived from the air electrode side interface.
  • the call call plot of the calculation target fuel cell obtained by performing the first step is composed of four arcs
  • the arc is on the side where the real part resistance value is larger than the third arc. Since the relationship between the first arc, the second arc, and the third arc does not change only by increasing, the call plot of the calculation target fuel cell obtained by performing the first step is The same as the case of three circles.
  • the method for measuring the interface resistance according to the second aspect of the present invention is to calculate the interface resistance by calculating the fuel electrode side interface resistance Ria and the air electrode side interface resistance Ric when the fuel cell for calculation is operated.
  • the complex impedance measurement of the calculation target fuel cell is performed under the third measurement condition and the fourth measurement condition that are different only in the gas composition of the air electrode side gas, and then the frequency in the third measurement condition is n.
  • the difference ⁇ R (3-4) rn between the real part resistance value R 3 rn and the real part resistance value R 4 rn when the frequency in the fourth measurement condition is n is expressed by the following equation (2):
  • An equivalent circuit having (i) a first resistor connected in series; (ii) a second resistor and a first capacitor connected in parallel; and (iii) a third resistor and a second capacitor connected in parallel.
  • the first step, the second step and the third step according to the method for measuring the interfacial resistance according to the second aspect of the present invention are the first step and the second step according to the method for measuring the interfacial resistance according to the first aspect of the present invention. And it is the same as that of a 3rd process.
  • the equivalent circuit is constructed.
  • the first When the call “call” plot of the cell for the fuel cell to be calculated obtained in the step is the call “call” plot 1 a shown in FIG. 1, that is, the calculation obtained in the first step.
  • the equivalent circuit to be constructed is the equivalent circuit 21 shown in Fig. 6.
  • the equivalent circuit 21 includes (i) a first resistor 22a, (ii) a second resistor 24a and a first capacitor 23a connected in parallel, and (iii) connected in parallel.
  • the third resistor 2 6 a and the second capacitor 2 5 a are connected in series.
  • fitting is performed between the equivalent circuit 21 and the cornole-conore plot 1 a of the senore for the calculation target fuel cell obtained in the first step.
  • input the circuit diagram of the equivalent circuit, the resistance value of the resistor in the equivalent circuit, the capacitance value of the capacitor in the equivalent circuit, and the reactance and calculate the Cole Cole plot and output the shape Use existing software that can.
  • the existing software used for the fitting is not particularly limited, and examples thereof include Z V i e w2 -E qu i v a l nt-C i rc u i ts.
  • the fitting is performed by first softening the circuit diagram of the equivalent circuit 21, the initial value of the first resistor 2 2 a, the initial value of the second resistor 24 a, and the initial value of the first capacitor 23 a Value, the initial value of the third resistor 26a, the initial value of the second capacitor 25a, and the input value necessary for the calculation of reactance, etc., and then changing the input value little by little
  • the calculation by the software is repeated, and the shape of the call / call plot obtained by the calculation by the software is changed to the call / call plot of the calculation target fuel cell obtained in the first step. This is done by approximating the shape of the G.
  • the shape of the call ⁇ call ⁇ plot obtained by the calculation in the software is the same as that of the cell for the fuel cell to be calculated obtained in the first step.
  • the input value when it matches or substantially matches the shape of the mouthpiece is obtained as the input value at the time of fitting.
  • the relationship between the equivalent circuit 21 and the Cole-Cole 'plot ⁇ a of the calculation target fuel cell obtained in the first step will be described by the second step and the third step.
  • the second resistance 24 a is a fuel electrode side interface resistance Ria
  • the first capacitor 23 a is a capacitor component at the fuel electrode side interface
  • the third resistance 26 a is an air electrode side interface resistance.
  • the second capacitor 25 a corresponds to the capacitor component at the air electrode side interface, respectively.
  • the first arc 2a of the Cole-Cole plot 1a is an arc derived from the air electrode side interface
  • the second arc 3a Is identified as a circular arc originating from the fuel electrode side interface
  • the second resistance 24 a is the air electrode side interface resistance R ic
  • the first capacitor 23 a is the capacitor component of the air electrode side interface.
  • the third resistor 26 a corresponds to the fuel electrode side interface resistance R ia
  • the second capacitor 25 a corresponds to the capacitor component on the fuel electrode side interface.
  • the input value of the second resistance 24 a is the fuel electrode side interface resistance Ria
  • the input value of the third resistance 26 a is the air electrode side interface resistance R ic.
  • the fitting The input value of the second resistance 24 a is the air electrode side interface resistance R ic
  • the input value of the third resistance 26 a is the fuel electrode side interface resistance R ia .
  • the equivalent circuit to be constructed is the equivalent circuit 30 shown in FIG.
  • the equivalent circuit 30 includes (i) a first resistor 2 2 b, (ii) a second resistor 2 4 b connected in parallel and a first capacitor 2 3 b, (iii) connected in parallel.
  • the third resistor 26b and the second capacitor 25b, and (iv) the fourth resistor 28b and the third capacitor 27b connected in parallel are connected in series.
  • the fitting is performed by first applying the soft circuit diagram of the equivalent circuit 30, the initial value of the first resistor 2 2 b, the initial value of the second resistor 24 b, and the first capacitor 23 b
  • Initial value initial value of the third resistor 26b, initial value of the second capacitor 25b, initial value of the fourth resistor 28b, initial value of the third capacitor 27b, reactance
  • the Cole-Cole plot of the calculation target fuel cell obtained in the first step is composed of two arcs, except that the input values necessary for the calculation are input. The input value at the time of fitting and fitting is obtained.
  • the relationship between the equivalent circuit 30 and the call cell call 'plot 1 b of the fuel cell to be calculated obtained in the first step will be described by the second step and the third step.
  • the second resistance 24 b is the fuel electrode side interface resistance Ria
  • the first capacitor 23 b is the capacitor component of the fuel electrode side interface
  • the third resistance 26 b is the air electrode side interface resistance.
  • the second capacitor 25 b corresponds to the capacitor component at the air electrode side interface.
  • the second process and the third process (4) the call ⁇
  • the first arc 2b of Cole 'plot 1b is an arc derived from the air electrode side interface and the second arc 3b is an arc derived from the fuel electrode side interface
  • the second arc 3b The resistance 24 b is the air electrode side interface resistance R ic
  • the first capacitor 23 b is the capacitor component of the air electrode side interface
  • the third resistance 26 b is the fuel electrode side interface resistance R ia
  • the second capacitor 25 b corresponds to the capacitor component on the fuel electrode side interface.
  • the input value of the second resistance 24 b is the fuel electrode side interface resistance R ia
  • the input value of the third resistance 26 b is the air electrode side interface resistance R ic.
  • the fitting Of the input values at the time the input value of the second resistance 24 b is the air electrode side interface resistance R ic, and the input value of the third resistance 26 b is the fuel electrode side interface resistance R ia .
  • the call / call plot of the calculation target fuel cell obtained in the first step is composed of four or more arcs, the equivalent shown in FIG. 7 regardless of the number of arcs. Fitting with circuit 30 can be performed.
  • the call of the cell for calculation target fuel cell obtained in the first step is Cole plot (1)
  • the first measurement condition and the second measurement condition are measurement conditions that differ only in the fuel concentration in the fuel electrode side gas
  • the third measurement condition and the fourth measurement condition in the third step are Preferably, the measurement conditions are different only in the oxygen concentration in the air electrode side gas.
  • the first measurement condition and the second measurement condition in the second step are measurement conditions that differ only in the hydrogen concentration in the fuel electrode side gas
  • the third measurement condition and in the third step It is particularly preferable that the fourth measurement condition is a measurement condition in which only the oxygen concentration in the air electrode side gas is different.
  • the first measurement condition and the second measurement condition in the second step Are the measurement conditions that differ only in the water vapor concentration in the fuel electrode side gas
  • the third measurement condition and the fourth measurement condition in the third step are the oxygen conditions in the air electrode side gas. More preferably, the measurement conditions differ only in concentration.
  • the complex impedance measurement of the cell for the fuel cell to be calculated and the The temperature at which the complex impedance measurement of the calculation target fuel battery cell in the third step is not particularly limited and is appropriately selected depending on the type of cell and the operating conditions, and is usually from 1 to 120 ° C. Yes, for example, in the case of a solid oxide fuel cell, the temperature is from 600 to 120 ° C.
  • the first step and the third step are carried out to perform the first step. It is possible to reliably identify the interface from which the first arc and the second arc in the call plot of the calculation target fuel cell obtained in the process are derived. Therefore, the interface of the first aspect of the present invention According to the calculation method of the resistance and the calculation method of the interface resistance according to the second aspect of the present invention, the fuel electrode side interface resistance and the resistance when the calculation target fuel cell is operated under a specific operating condition desired to be calculated. The air electrode side interface resistance can be calculated.
  • a slurry for forming a fuel electrode containing a mixed powder of nickel oxide (N i O) and scandiaceria stabilized zirconia (10 S c 1 C e SZ) having a mixing ratio of 50:50 was prepared, Using the slurry for forming the fuel electrode, a slurry layer for forming the fuel electrode with a film thickness of 100 ⁇ m was formed by screen printing. After drying, the slurry was fired at 1400 ° C for 5 hours to produce a fuel electrode.
  • the complex impedance of the fuel cell A is determined under the conditions that the operating temperature of the cell is 100 ° C. and the gas composition is the hydrogen concentration of the fuel electrode side gas and the oxygen concentration of the air electrode side gas shown in Table 1.
  • Measurement mode potentiostat, set voltage: 0.0 V, current range: 10 A, delay time: 0.1 sec, number of sweep measurement data: 50 times, integration number: 10 times maximum frequency: 1 0 0 k H Z, minimum frequency:. 0 1 H z, sinusoidal voltage:. 0 0 3 V rms, EM measurement time: 5 seconds, the polarization retention time:. 0 were measured at 2 seconds.
  • the results are shown in Tables 2-5.
  • Cole-Cole 'plots for measurements 1 to 4 are shown in Figs.
  • the operating condition for calculating the interfacial resistance in the first process is set as measurement 1
  • the first measurement condition in the second process is measured 4
  • the second measurement condition is measured 2
  • the third measurement condition in the third process is measured 1
  • the fourth measurement condition is set as measurement 2
  • the real part resistance difference No. 2 -Draft and real part resistance difference second graph was obtained. The results are shown in Tables 6 and 12. .
  • the second arc 32 which is the arc including the point of frequency 1 OH z, is the arc originating from the air electrode side among the arcs in the call, call, and plot of measurement 1 in Fig. 8. It can be recognized that there is.
  • the equivalent circuit shown in Fig. 7 was constructed. From the result of the above-mentioned arc recognition, in FIG. 7, the second resistance 24 b corresponds to the fuel electrode side interface resistance R i a, and the third resistance 26 b corresponds to the air electrode side interface resistance R i c. Next, using the existing software ZV ie w2—Equivalent—Circuits, fitting was performed with the call-call-plot of measurement 1 shown in Fig. 8, and the call 'call' plot shown in Fig. 13 was obtained. . The input value of the second resistor 24b in the case of the Cole-Cole-plot shown in Figure 1 is 0.99697.
  • the input value of the third resistor 26 b was 0.555527 ⁇ . Accordingly, the fuel cell A has a gas composition with a hydrogen concentration of 10 0 on the fuel electrode side.
  • the fuel electrode side interface resistance of the fuel cell A Is 0.969 76 ⁇ , interface resistance on the air electrode side R ic is 0.5 552
  • the interfacial resistance of the fuel cell can be ascertained under operating conditions, so that it is easy to construct a power generation system having the fuel cell.

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Abstract

La présente invention concerne un procédé de calcul de résistance d'interface dans lequel l'impédance complexe d'une pile pour une pile à combustible objet du calcul est mesurée dans des conditions de mesure où seule la composition en gaz du gaz du côté du pôle de combustible est différente et dans des conditions de mesure où seule la composition en gaz du gaz du côté du pôle d'air est différente de façon à obtenir un graphique de la différence de la partie réelle de la résistance, une décision est alors prise à partir de l'interface du côté du pôle de combustible et de l'interface du côté du pôle d'air, un arc dans le graphique de la courbe d'appel de la pile pour une pile à combustible objet du calcul est dérivé dans des condition de fonctionnement, la résistance de l'interface du côté du pôle de combustible Ria et la résistance de l'interface du côté du pôle d'air Ric sont déterminées à partir du graphique de la courbe d'appel ou déterminées en réalisant un ajustage sur le graphique de la courbe d'appel et un circuit équivalent. La résistance d'interface peut être calculée même si l'épaisseur de l'électrolyte dans la pile pour la pile à combustible est petite ou l'aire ou le profil au niveau du joint n'est pas identique du côté du pôle de combustible et du côté du pôle d'air.
PCT/JP2006/307161 2006-03-29 2006-03-29 Procede de calcul de la resistance d'interface WO2007110970A1 (fr)

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WO2010128555A1 (fr) * 2009-05-08 2010-11-11 トヨタ自動車株式会社 Dispositif d'estimation de la concentration en hydrogène d'une pile à combustible et système de pile à combustible
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JP2013229349A (ja) * 2013-07-19 2013-11-07 Yokogawa Electric Corp インピーダンス特性評価方法およびインピーダンス特性評価装置
JP2015022884A (ja) * 2013-07-18 2015-02-02 アイシン精機株式会社 固体酸化物形燃料電池単セルに係る各抵抗値を導出する導出方法および導出装置
JP2018517239A (ja) * 2015-04-23 2018-06-28 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 燃料電池において過電圧を求める方法
JP2018147657A (ja) * 2017-03-03 2018-09-20 株式会社京三製作所 燃料電池の診断装置、燃料電池システム及び診断方法
JP2019053078A (ja) * 2014-04-14 2019-04-04 日置電機株式会社 測定装置および測定方法
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JP2009180717A (ja) * 2008-02-01 2009-08-13 Mitsui Eng & Shipbuild Co Ltd シリコン薄膜の評価方法
JP5338903B2 (ja) * 2009-05-08 2013-11-13 トヨタ自動車株式会社 燃料電池の水素濃度推定装置、燃料電池システム
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JP2013229349A (ja) * 2013-07-19 2013-11-07 Yokogawa Electric Corp インピーダンス特性評価方法およびインピーダンス特性評価装置
JP2019053078A (ja) * 2014-04-14 2019-04-04 日置電機株式会社 測定装置および測定方法
JP2018517239A (ja) * 2015-04-23 2018-06-28 フォルシュングスツェントルム・ユーリッヒ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 燃料電池において過電圧を求める方法
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JP2018147657A (ja) * 2017-03-03 2018-09-20 株式会社京三製作所 燃料電池の診断装置、燃料電池システム及び診断方法
CN114976131A (zh) * 2022-06-14 2022-08-30 哈尔滨工业大学（深圳） 一种高温质子交换膜燃料电池性能测试系统及其方法
CN114976131B (zh) * 2022-06-14 2023-02-28 哈尔滨工业大学（深圳） 一种高温质子交换膜燃料电池性能测试系统及其方法

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