JP6074759B2 - Deterioration judgment method and degradation judgment device for lead acid battery - Google Patents

Description

The present invention relates to a deterioration determination method and a deterioration determination device for a lead storage battery that can be repeatedly used by charging.

  A lead storage battery is generally used as a secondary battery that can be repeatedly used by charging. In lead-acid batteries, sulfation is deposited on the negative electrode plate by repeated charge and discharge. The sulfation is a spongy lead sulfate crystal and has low solubility, and when deposited on the negative electrode plate, the reaction area of the negative electrode plate is reduced, leading to deterioration of the lead storage battery and hindering charging. For these reasons, it has been conventionally performed to determine the deterioration of a lead storage battery. In this deterioration judgment, an alternating current impedance measuring method for measuring an internal impedance in the storage battery by applying an alternating voltage is frequently used.

  The AC impedance measurement method measures the internal impedance that changes according to the frequency of the AC voltage by applying AC to the storage battery, and can be measured using the positive and negative electrodes in the storage battery without disassembling the storage battery. Good. Patent Document 1 discloses a conventional method for determining deterioration of a lead storage battery by an AC impedance measurement method.

The deterioration determination described in Patent Document 1 is performed by changing the frequency of an alternating current supplied to a storage battery (lead storage battery) , measuring the impedance of each frequency to obtain a frequency characteristic curve of the impedance, and reactance based on the frequency characteristic curve. The impedance at which the component becomes zero is obtained, and the deterioration of the storage battery is determined based on this impedance value.

JP 2007-333494 A

In general, in the impedance measured by a lead storage battery , the resistance of the electrode plate appears as an actual resistance component, and the resistance of charge transfer between the electrode plate and the electrolytic solution appears as a reactance component. As the number of times of charging the lead storage battery increases, the internal resistance increases, and both the actual resistance component and the reactance component increase. In the deterioration determination described in Patent Document 1, measurement is performed at a frequency at which the reactance component of the impedance becomes zero. However, even when the reactance component that increases with the number of times of charging is set to zero, the actual resistance component has a high value. Yes. Therefore, even if the deterioration is determined based on the impedance value with the reactance component being zero, it is difficult to determine the deterioration with high accuracy.

The present invention has been made in view of such problems, and an object of the present invention is to provide a deterioration determination method and a deterioration determination device for a lead storage battery that can determine the deterioration of the lead storage battery with high accuracy. To do.

The deterioration judgment method of the lead storage battery of the present invention measures the impedance of each frequency by supplying and discharging the alternating current with the frequency changed to the lead storage battery , detects the phase difference of the impedance from the measured value, Create a phase difference curve in which the phase difference is plotted against the frequency , calculate the phase difference area determined by the phase difference curve within a predetermined frequency range, and degrade the lead-acid battery based on the calculated phase difference area It is characterized by judging.

In this case, the phase difference of the impedance detection with respect to the measurement lead-acid battery and the reference lead-acid battery, after creating the phase difference curve for the measured lead-acid battery and the reference lead-acid battery, the phase difference curve of the reference lead battery measured It is preferable to determine the difference between the lead storage battery and the phase difference curve within a predetermined frequency range, and to determine the deterioration of the measured lead storage battery by comparing the difference curve area determined by the difference between the phase difference curves.

Another method of determining deterioration of a lead storage battery according to the present invention is to measure the impedance of each frequency by supplying and discharging an alternating current whose frequency is changed to the lead storage battery , and the actual resistance component of the impedance for each measured frequency and The reactance component is plotted on a Smith chart to create an impedance locus, and deterioration of the lead storage battery is determined based on the impedance locus.

In this case, the impedance locus created for measuring lead-acid battery and the reference lead-acid battery, it is preferable to determine the deterioration of the measurement lead-acid battery by comparing an impedance locus of the measured lead-acid battery and the reference lead-acid battery.

In the above-described method for judging deterioration of a lead storage battery , it is preferable to change the alternating current within a frequency range of 0.1 to 1 kHz.

The deterioration determination device for a lead storage battery according to the present invention includes a frequency control unit that changes a frequency of an alternating current, a current supply unit that supplies and discharges the alternating current whose frequency is changed by the frequency control unit to the lead storage battery , and the discharge An impedance measurement unit that measures the impedance of the lead-acid battery that varies depending on the phase, a phase difference detection unit that detects the phase difference of the impedance by synchronously detecting the reference signal from the frequency control unit and the measurement signal from the impedance measurement unit, and A deterioration determination unit that determines deterioration of the lead storage battery using the phase difference of the phase difference detection unit as an index, and the deterioration determination unit represents a phase difference curve in which the phase difference of the impedance is plotted against the frequency. A phase difference curve calculation unit to calculate, and a phase difference area determined by the phase difference curve within a predetermined frequency range were calculated and calculated Characterized in that it is formed by a determining section for determining deterioration based on the phase difference area.

The phase difference detection unit detects the phase difference of the impedance with respect to the measurement lead storage battery and the reference lead storage battery, and the phase difference curve calculation unit creates the phase difference curve with respect to the measurement lead storage battery and the reference lead storage battery . The determination unit obtains a difference between the phase difference curve of the reference lead acid battery and the phase difference curve of the measured lead acid battery within a predetermined frequency range, and determines the difference curve area determined by the difference between the phase difference curves. It is preferable to determine the deterioration of the measured lead-acid battery based on it.

Another lead storage battery degradation determination device of the present invention includes a frequency control unit that changes the frequency of an alternating current, a current supply unit that supplies and discharges the alternating current whose frequency has been changed by the frequency control unit to the lead storage battery , An impedance measurement unit that measures the impedance of the lead storage battery that changes due to the discharge; and an impedance locus calculation unit that calculates an impedance locus by plotting an actual resistance component and a reactance component of the impedance measured by the impedance measurement unit on a Smith chart; And a deterioration determination unit that determines deterioration of the lead-acid battery based on the impedance locus determined by the impedance locus calculation unit.

In this case, the impedance locus calculating unit plots the actual resistance component and the reactance component of the measurement lead storage battery and the reference lead storage battery on the Smith chart, and calculates the impedance locus for the measurement lead storage battery and the reference lead storage battery . Is preferred.

In the above lead acid battery deterioration determination device, the frequency control unit preferably changes the alternating current in a frequency range of 0.1 to 1 kHz.

According to the deterioration determination method for a lead storage battery of the present invention, since the impedance of the lead storage battery is measured within a wide frequency range, the deterioration of the lead storage battery can be easily determined. Further, to evaluate the deterioration of the lead storage battery by integrating the phase difference curve, or to evaluate the deterioration of the lead storage battery from the impedance locus to calculate the trajectory area, improved quantitative accuracy of the deterioration degree. Thereby, deterioration judgment of a lead storage battery can be performed with high accuracy.

According to the deterioration determination device for a lead storage battery of the present invention, the above deterioration determination can be suitably performed.

It is a graph which shows the phase difference at the time of discharging a lead storage battery at a fixed frequency. It is a graph which shows the impedance according to the change of a frequency. It is a graph which shows the phase of the impedance according to the change of a frequency. It is a graph which shows a phase difference curve. It is a block diagram which shows the deterioration determination apparatus of a lead storage battery . It is a block diagram which shows the deterioration determination apparatus of another lead acid battery . It is a front view which shows a Smith coordinate. It is a front view which shows the impedance locus | trajectory plotted on the Smith chart. It is a front view explaining the case where a locus area is calculated from an impedance locus.

  The inventors measured an actual resistance component and a reactance component at a constant frequency (1 kHz) when an alternating current was supplied to a lead storage battery and discharged. FIG. 1 is a graph showing the measurement results. The characteristic curve A is a lead storage battery having a CCA value of 270, the characteristic curve B is charged and regenerated, and the lead storage battery having a CCA value of 230 is deteriorated. This is a lead storage battery having a CCA value of 170. The CCA value is a cold cranking ampere, and the larger the CCA value, the higher the engine start performance.

Arrow lines A1, B1, and C1 in FIG. 1 indicate the phase difference (phase angle) between the voltage and current at the initial stage of discharge of the characteristic curves A, B, and C, respectively. The phase difference of the arrow line A1 is the largest, the phase difference of the arrow line C1 is the smallest, and it is shown that the phase difference corresponds to the magnitude of the CCA value. In other words, the phase difference of the lead storage battery corresponds to the CCA value, and the larger the phase difference (that is, the larger the CCA value), the less deterioration of the lead storage battery. From this, it can be understood that the phase difference at the time of discharging can be used as an index of deterioration of the lead storage battery. The present invention has been made based on such knowledge.

The method of judging the deterioration lead-acid battery of one embodiment of the present invention measures the impedance of each frequency by discharging an alternating current with varying frequency is supplied to the lead-acid battery, the phase difference of the impedance from the measured value Detecting and creating a phase difference curve in which the phase difference is plotted against frequency, and judging deterioration of the lead-acid battery based on a phase difference area determined by the phase difference curve within a predetermined frequency range. is there.

Such a deterioration judgment method is not to set the alternating current applied to the lead storage battery to a fixed frequency, but to apply and discharge an alternating current having a wide range of frequencies to the lead storage battery . It is characterized in that the frequency is obtained. In addition, for a wide range of frequencies generated by the application of alternating current, the phase difference of the impedance of each frequency is detected, a phase difference curve is created based on this phase difference, and based on the created phase difference curve It is characterized in that the deterioration of the lead storage battery is judged.

In this deterioration determination, detects the phase difference of the impedance with respect to the measurement lead-acid battery and the reference lead-acid battery, after creating a phase difference curve for the measured lead-acid battery and the reference lead-acid battery, and the phase difference curve of the reference lead-acid battery It is good to determine the difference between the measured lead-acid battery phase difference curve within a predetermined frequency range and compare the difference curve area determined by this phase difference curve difference to judge the deterioration of the lead-acid battery. is there.

Figure 2 is a graph plotting the impedance of each frequency obtained by discharging a wide range of lead-acid battery by supplying an alternating current having a frequency with respect to lead-acid batteries, lead-acid battery characteristic curve M is CCA value 275 The characteristic curve N is the impedance for a lead-acid battery with a CCA value of 215. As shown in the figure, the impedance changes in a wide frequency range of 0.1 Hz to 1 kHz. In this embodiment, the deterioration of the lead storage battery is determined based on the impedance change in this wide range of frequencies. FIG. 3 is a graph in which the phase with respect to the frequency is plotted based on FIG. 2, the characteristic curve D shows the lead storage battery D with the CCA value 275, and the characteristic curve E shows the lead storage battery E with the CCA value 215. The horizontal axis in FIG. 3 is the frequency axis and is displayed on the logarithmic axis.

In FIG. 3, a lead storage battery D having a large CCA value can be used as a reference lead storage battery when determining deterioration, and a lead storage battery E having a small CCA value can be used as a measurement lead storage battery requiring deterioration determination. From these characteristic curves D and E, the phase difference between voltage and current at each frequency is calculated. The characteristic curve F is a plot of values obtained by performing a calculation by subtracting the phase difference of the lead storage battery E from the calculated phase difference of the lead storage battery D. Therefore, the characteristic curve F is a phase difference curve in which the phase difference of the measured lead storage battery E with respect to the phase difference of the reference lead storage battery D is plotted against the frequency. The difference value of the phase difference curve F is the right axis of FIG. 3, and the unit is rad.

After creating the phase difference curve F, the phase difference area determined by the phase difference curve F is calculated within the measured frequency range (in the range of about 0.1 to 1 kHz in FIG. 3). The calculated phase difference area represents the degree to which the measured lead storage battery E has deteriorated with respect to the reference lead storage battery D. For this reason, the deterioration of the measured lead storage battery E can be determined based on the calculated phase difference area.

  The calculation of the phase difference area is performed by integrating the area of the phase difference curve F with respect to the frequency axis (horizontal axis) within a frequency range of about 0.1 to 1 kHz. This calculation need not be performed within the above frequency range, but can be performed within an appropriate frequency range. That is, it is possible to select and perform a frequency range that is easy to calculate and in which the difference can be a clear numerical value. In this embodiment, it is preferable to calculate within a frequency range of 100 to 2000 Hz as will be described later.

4 is a graph in which the horizontal axis in the graph of FIG. 3 is converted from a logarithmic axis to a normal real axis and the characteristic curve F of FIG. 3 is plotted. The characteristic curve F of FIG. Become. The characteristic curve G is the same as the characteristic curve F, and is a phase difference curve G obtained by subtracting the phase difference of the lead storage battery E from the phase difference of the lead storage battery D in FIG.

After creating the phase difference curve G, the phase difference area is calculated within the frequency range where the phase difference can be clearly calculated from the graph of FIG. In FIG. 4, the frequency range of about 100 to 2000 Hz is clear, and the phase difference area within this range is calculated by integration. Then, the deterioration of the lead storage battery is determined based on the calculated phase difference area. That is, the phase difference area is calculated by integrating a value obtained by subtracting the phase difference of the lead storage battery E from the phase difference of the lead storage battery D. Therefore, the calculated phase difference area is calculated by the measurement lead storage battery E using the reference lead storage battery D. The degree of deterioration of the measured lead storage battery E can be grasped by the size of the phase difference area.

According to the deterioration determination of such lead storage battery, not to measure the impedance of the lead-acid battery in only the frequency of a particular fixed value, for measuring the impedance of the lead-acid battery in a range of a wide range of frequencies, the phase difference The integrated value of the phase difference area is larger than (phase angle, FIG. 1). For this reason, it is possible to easily determine the deterioration of the lead storage battery . Further, since the deterioration of the lead storage battery is evaluated by integrating the phase difference curve, the quantitative accuracy of the degree of deterioration is improved. Thereby, deterioration judgment of a lead storage battery can be performed with high accuracy.

In this embodiment, the deterioration of the lead storage battery is determined based on the difference between the phase difference of the reference lead storage battery D and the phase difference of the measured lead storage battery E. However, the present invention is not limited to this, and becomes a determination criterion for deterioration. A threshold value may be set in advance, and deterioration may be determined by comparison with this threshold value. The determination in this case is to create a phase difference curve from the characteristic curve E in FIG. 2, calculate the phase difference area based on the phase difference curve within a predetermined frequency range, and compare the calculated phase difference area with a threshold value. Can be performed.

FIG. 5 shows a deterioration determination apparatus 1 used for deterioration determination of this embodiment. Reference numeral 2 denotes a lead storage battery to be measured. Since the lead storage battery 2 holds a voltage therein, the deterioration determination device 1 has a structure in which impedance is measured by an AC four-terminal method. The deterioration determination device 1 is for determining deterioration by connecting two input / output terminals to each of the terminals 3 and 3 of the lead storage battery 2, and includes a frequency control unit 5, a current supply unit 6, an impedance It has a measurement unit 7, a phase difference detection unit 8, and a deterioration determination unit 9.

The frequency control unit 5 changes the frequency of the alternating current supplied to the lead storage battery 2, and a sweep oscillation circuit 11 is used. The sweep oscillation circuit 11 is a circuit that continuously changes the frequency from a low frequency to a high frequency. The frequency changed by the sweep oscillation circuit 11 is supplied to the current supply unit 6.

The current supply unit 6 supplies an alternating current having a changed frequency to the lead storage battery 2, and the lead storage battery 2 is discharged by the supply of the alternating current. The current supply unit 6 includes a sweep waveform amplitude control circuit 12 connected to the sweep oscillation circuit 11 and an output amplifier 13 connected to the circuit 12, and the output amplifier 13 is connected to one terminal 3 of the lead storage battery 2. The sweep waveform amplitude control circuit 12 is connected to a rectifying / smoothing / integrating circuit 15 connected to the current-voltage conversion circuit 14.

The impedance measuring unit 7 measures the impedance of the lead storage battery 2 that changes due to discharge at each frequency. As the impedance measuring unit 7, a voltage differential amplifier 17 connected to the other terminal 3 of the lead storage battery 2 is used.

  The phase difference detection unit 8 receives the measurement signal from the voltage differential amplifier 17 and the reference signal from the sweep oscillation circuit 11, thereby synchronously detecting these signals and the synchronously detected detection signal. And a phase difference detection circuit 19 for detecting a phase difference based on the above. By the synchronous detection by the synchronous detector 18, the phase difference φ is output to the phase difference detection circuit 19 as a value of cos φ, for example, and the phase difference detection circuit 19 detects the phase difference based on this. Thereby, the phase difference detector 8 detects the phase difference of each frequency from the impedance of each frequency.

The deterioration determination unit 9 determines deterioration of the lead storage battery 2 using the phase difference of each frequency detected by the phase difference detection unit 8 as an index. The deterioration determination unit 9 is formed by a phase difference curve calculation unit 21 and a determination unit 22. The phase difference curve calculation unit 21 is a calculation unit that calculates a phase difference curve (characteristic curve F or G) in which the phase difference of the impedance is plotted against the frequency. The determination unit 22 calculates a phase difference area determined by the phase difference curve calculated by the phase difference curve calculation unit 21 within a predetermined frequency range, and determines deterioration of the lead storage battery 2 based on the calculated phase difference area. . This determination is made by comparison with the phase difference area of the reference lead-acid battery D as described above, or by comparison with a predetermined threshold value set in advance.

Next, another embodiment of the present invention will be described. The deterioration judgment method of this embodiment measures the impedance of each frequency by supplying an alternating current whose frequency is changed to a lead storage battery and discharging it, and calculates the actual resistance component and reactance component of the impedance for each measured frequency. An impedance locus is created by plotting on the Smith chart, and the deterioration of the lead storage battery is determined based on the impedance locus.

The deterioration judgment method of this embodiment does not set the alternating current applied to the lead storage battery to a fixed frequency as in the above embodiment, but applies and discharges an alternating current of a wide range of frequencies to the lead storage battery , The impedance is measured in a wide range. In addition, this embodiment is characterized in that the impedance obtained by the discharge is plotted on a Smith chart and an impedance locus is created to determine deterioration.

In determining the deterioration of the lead storage battery , it is preferable to create an impedance locus for the measurement lead storage battery and the reference lead storage battery, and to determine the deterioration of the lead storage battery based on the impedance locus of the measurement lead storage battery and the reference lead storage battery .

FIG. 6 shows a deterioration determination device 1A used in this embodiment. 5 is different from the deterioration determination device 1 in FIG. 5 in that an impedance locus calculation unit 31 is connected to the voltage differential amplifier 17 constituting the impedance measurement unit 7, and a deterioration determination unit 32 is connected to the impedance locus calculation unit 31. The frequency control unit 5 and the current supply unit 6 are the same as those of the deterioration determination device 1 in FIG. Therefore, in the deterioration determination device 1A, the alternating current whose frequency has changed in a wide range is supplied to the lead storage battery 2 and discharged, and the impedance that changes due to the discharge is measured corresponding to each frequency. It is the same as the device 1. The frequency range of the alternating current to be supplied can be appropriately selected within the range of 0.1 to 1 kHz.

The impedance locus calculation unit 31 plots the actual resistance component and reactance component of the impedance measured by the impedance measurement unit 7 on a Smith chart to calculate the impedance locus. The deterioration determination unit 32 determines the deterioration of the lead storage battery 2 based on the impedance locus.

  FIG. 7 shows Smith coordinates. When the impedance is expressed as Rs + jRx, the actual resistance component of the impedance is plotted on the Rs coordinate. The Rs coordinate is zero at the left end and infinite at the right end. A circle Rx in FIG. 7 is a constant resistance circle having a constant actual resistance component, and a numerical value Rx of the reactance component is plotted. These plots create an impedance locus on the Smith chart.

Figure 8 shows the impedance locus created Smith chart, the locus H impedance locus by the discharge of the lead-acid battery CCA value 270, the locus K is the impedance locus by the discharge of the lead-acid battery CCA value 175. In this embodiment, a lead storage battery having a large CCA value (CCA value 270) is used as a reference lead storage battery in the determination of deterioration, and a lead storage battery having a small CCA value (CCA value 175) is used as a measurement lead storage battery that requires deterioration determination. Can do.

As a result of examining the impedance locus of the Smith chart and the CCA value of the lead storage battery , the present inventors confirmed that the impedance locus tends to converge toward the inside as the CCA value decreases, that is, as the deterioration progresses. Yes. In FIG. 8, the impedance locus K ( measured lead-acid battery ) converges inward with respect to the impedance locus H of the reference lead-acid battery , and deterioration of the measured lead-acid battery can be determined based on the degree of convergence to the inside. .

According to the deterioration determination of such embodiments, measuring the impedance of the lead-acid battery in a range of a wide range of frequencies, to create an impedance locus plot of the impedance Smith chart, lead based on the impedance locus It is possible to easily determine the deterioration of the storage battery . In addition, since the deterioration of the lead storage battery is evaluated from the degree of convergence of the impedance locus, the quantitative accuracy of the degree of deterioration is improved. Therefore, the deterioration judgment of the lead storage battery can be performed with high accuracy.

In this embodiment, it is also possible to determine the deterioration of the lead-acid battery based on the locus area determined by the impedance locus in addition to the impedance locus on the Smith chart. FIG. 9 shows a case where the locus area is determined by the impedance locus H, K. The trajectory area can be calculated by integrating the area surrounded by a line connecting the start point and the end point plotted on the Smith chart by determining the frequency range used for measurement.

The area P in FIG. 9 is the locus area of the impedance locus H, and the area Q is the locus area of the impedance locus K. As described above, since the impedance trajectory converges as the deterioration progresses, the magnitudes of the trajectory areas P and Q correspond to the magnitude of the CCA value, that is, the degree of progress of the degradation. Therefore degradation determination unit 32 are two loci area P, by comparing the Q, is possible to determine the degree of deterioration of the measurement lead-acid battery (a lead-acid battery of CCA values 175) with respect to the reference lead-acid battery (a lead-acid battery CCA value 270) it can. As described above, the deterioration of the lead storage battery can be easily determined also by the deterioration determination based on the locus area of the impedance locus. In this case, since the deterioration of the lead storage battery is evaluated by the numerical value of the locus area, the quantitative accuracy of the deterioration degree is improved.

In this embodiment, the deterioration of the lead storage battery is determined based on the difference between the impedance locus of the reference lead storage battery and the impedance locus of the measured lead storage battery . However, the present invention is not limited to this, and a threshold value that is a criterion for determining deterioration. May be set in advance, and deterioration may be determined by comparison with this threshold value. The determination in this case can be made by calculating the impedance locus of the measured lead-acid battery within a predetermined frequency range and comparing this impedance locus with a threshold value.
The

DESCRIPTION OF SYMBOLS 1, 1A Degradation judgment apparatus 2 Lead acid battery 5 Frequency control part 6 Current supply part 7 Impedance measurement part 8 Phase difference detection part 9, 32 Degradation judgment part 21 Phase difference curve calculation part 22 Determination part 31 Impedance locus calculation part F, G rank Phase difference curve H, K Impedance locus P, Q locus area

Claims (10)

The impedance of each frequency is measured by supplying an alternating current with a changed frequency to the lead storage battery and discharged, the phase difference of the impedance is detected from the measured value, and the phase difference is plotted against the frequency. A lead-acid battery characterized by creating a curve, calculating a phase difference area determined by the phase difference curve within a predetermined frequency range, and judging deterioration of the lead-acid battery based on the calculated phase difference area Degradation judgment method. A method for judging deterioration of a lead storage battery according to claim 1,
The phase difference between the impedances detected for the measurement of lead-acid battery and the reference lead-acid battery, after creating the phase difference curve for the measured lead-acid battery and the reference lead-acid battery, the reference lead-acid battery and retardation curves of the measured lead-acid battery A lead storage battery characterized in that a difference between a phase difference curve and a difference curve area determined by the difference between the phase difference curves is determined within a predetermined frequency range, and the deterioration of the measured lead storage battery is judged. Degradation judgment method. The impedance of each frequency is measured by supplying an alternating current of varying frequency to the lead storage battery and discharging it, and the impedance resistance locus is plotted by plotting the actual resistance component and reactance component of the measured impedance for each frequency on a Smith chart. A method for determining deterioration of a lead storage battery , characterized in that the deterioration of the lead storage battery is determined based on the impedance locus. A method for judging deterioration of a lead storage battery according to claim 3,
Wherein the impedance locus was created for the measurement lead-acid battery and the reference lead-acid battery, the measuring lead acid battery and lead-acid battery deterioration determination, characterized in that by comparing the impedance locus of the reference lead-acid battery to determine the deterioration of the measurement lead storage battery Method.   The deterioration determination method for a lead storage battery according to any one of claims 1 to 4, wherein the alternating current is changed in a frequency range of 0.1 to 1 kHz. A frequency controller that changes the frequency of the alternating current;
A current supply unit for supplying and discharging an alternating current whose frequency has been changed by the frequency control unit to the lead-acid battery ;
An impedance measuring unit for measuring the impedance of the lead storage battery that changes due to the discharge;
A phase difference detection unit for detecting a phase difference of impedance by synchronously detecting a reference signal from the frequency control unit and a measurement signal from the impedance measurement unit;
A deterioration determination unit that determines deterioration of the lead-acid battery using the phase difference of the phase difference detection unit as an index, and
The deterioration determining unit includes a phase difference curve calculating unit that calculates a phase difference curve in which the phase difference of the impedance is plotted with respect to the frequency, and a phase difference area determined by the phase difference curve within a predetermined frequency range. And a determination unit that determines deterioration based on the calculated phase difference area . A deterioration determination device for a lead storage battery , characterized in that: It is a deterioration judgment apparatus of the lead storage battery according to claim 6 ,
The phase difference detection unit detects the phase difference between the impedance to measure lead-acid battery and the reference lead-acid battery, the phase difference curve calculation unit creates the phase difference curve for the measured lead electric storage batteries and reference lead-acid battery The determination unit obtains a difference between the phase difference curve of the reference lead acid battery and the phase difference curve of the measured lead acid battery within a predetermined frequency range, and is based on the difference curve area determined by the difference of the phase difference curve. And determining the deterioration of the lead acid storage battery . A frequency controller that changes the frequency of the alternating current;
A current supply unit for supplying and discharging an alternating current whose frequency has been changed by the frequency control unit to the lead-acid battery ;
An impedance measuring unit for measuring the impedance of the lead storage battery that changes due to the discharge;
An impedance trajectory calculating unit that calculates an impedance trajectory by plotting the actual resistance component and reactance component of the impedance measured by the impedance measuring unit on a Smith chart;
A deterioration determination device for a lead storage battery , comprising: a deterioration determination unit that determines deterioration of the lead storage battery based on the impedance locus determined by the impedance locus calculation unit. It is a deterioration judgment apparatus of the lead storage battery according to claim 8 ,
The impedance locus calculation unit plots the actual resistance component and reactance component of the measurement lead storage battery and the reference lead storage battery on the Smith chart and calculates the impedance locus for the measurement lead storage battery and the reference lead storage battery . Deterioration judgment device for lead storage battery . The lead-acid battery deterioration determination device according to claim 6 or 8 , wherein the frequency control unit changes the alternating current in a frequency range of 0.1 to 1 kHz.

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