Battery by-product deposit removal device and system

Abstract

To efficiently remove by-product deposits generated on the electrodes of a storage battery. [Solution] The system of this embodiment comprises a power supply capable of charging a storage battery and a by-product deposit removal device for removing by-product deposits generated on the electrodes of the storage battery, wherein the by-product deposit removal device comprises a removal signal generation unit that generates a by-product deposit removal signal using a current taken from the power supply, at least when the power supply is charging the storage battery, and an electrode connection unit that outputs the removal signal to the electrodes of the storage battery.

Description

Technical Field

[0004] , , , , , , , , , , , , , , , ,

[0005]

[0001] The present invention relates to a system including a by-product deposit removing device for removing by-product deposits generated on electrodes of a storage battery.

Background Art

[0002] Storage batteries are widely used. The deterioration of a storage battery is roughly classified into two types: cycle deterioration due to repeated charge and discharge, and storage deterioration due to the storage period. However, both are deteriorations caused by the deposition of by-products on the electrodes. The deposition of by-products is caused by electrolyte decomposition and self-discharge in a high-temperature environment, overcharging, over-discharging, etc., resulting in an increase in internal resistance, causing a decrease in capacity and a risk of internal short circuit.

[0003] Regarding the technology for preventing and removing by-product deposits generated on electrodes of a storage battery, for example, by adding a carbon material to lead (Pb), which is an electrode material of a lead storage battery, or using a surfactant, a metal ion adjuster, etc. in the electrolyte, an effect can be obtained, but in most cases, it does not reach complete prevention or removal, which is a problem. Also, as disclosed in Patent Document 3, a technology for generating a removal signal using the current taken out from the electrode of a storage battery and removing by-product deposits is known.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0006] Furthermore, in conventional configurations that generate a removal signal using current extracted from the electrodes of a storage battery, the power of the storage battery is consumed in conjunction with the generation of the removal signal, raising concerns about a decrease in the battery's charge level. Another objective of the present invention is to efficiently remove by-product deposits while suppressing the power consumption of the storage battery. [Means for solving the problem]

[0007] To solve the above problems, the present invention provides a system comprising a power source capable of charging a storage battery and a by-product deposit removal device for removing by-product deposits generated on the electrodes of the storage battery, wherein the by-product deposit removal device comprises a removal signal generation unit that generates a by-product deposit removal signal using a current taken from the power source, at least when the power source is charging the storage battery, and an electrode connection unit that outputs the removal signal to the electrodes of the storage battery.

[0008] According to the present invention, since a removal signal is generated using current taken from a power source that can recharge the battery, by-product deposits generated on the electrodes of the battery can be efficiently removed without consuming the battery's power.

[0009] In the present invention, it is preferable that the removal signal generation unit generates the removal signal using the current drawn from the power supply, even when the battery has been fully charged by the power supply. By continuing to generate the removal signal even after charging is complete, the removal effect of by-product deposits can be enhanced.

[0010] In the present invention, the removal signal preferably includes a pulsed current having a frequency of 5 kHz to 50 kHz. By using a pulsed current in this frequency band, by-product deposits can be effectively removed.

[0011] In the present invention, it is preferable that the electrode connection part outputs the rejection signal with a current of 3mA to 2A.

[0012] In the present invention, the removal signal consists of a periodic pulse current, and when the amplitude value of the rising edge of a single pulse current waveform of the removal signal is H1, and the amplitude value of the undershoot after the falling edge of the pulse current waveform is H2, it is preferable that H2 is 0.2 to 1.0 times H1, and when the time width of the rising edge of the pulse current waveform is T1, and the time width of the falling edge accompanied by the undershoot is T2, it is preferable that T2 is 0.02 to 0.2 times T1. By using a pulse current having such waveform characteristics, by-product deposits can be efficiently removed without damaging the electrodes.

[0013] In the present invention, the pulse current waveform preferably includes a ringing waveform following the undershoot, and the time width T3 of the ringing waveform is preferably 2 to 10 times T2. The inclusion of ringing in the pulse current imparts micro-vibrations to the by-product deposits, thereby promoting their redissolution (reduction) in the electrolyte. Furthermore, it is possible to prevent the adhesion (crystallization) of by-products.

[0014] Furthermore, the by-product deposit removal device according to the present invention is a by-product deposit removal device for removing by-product deposits generated on the electrodes of a storage battery, and is characterized by comprising: a removal signal generation unit that generates a removal signal for the by-product deposits using a current taken from a power source different from the storage battery; and an electrode connection unit that inputs the removal signal to the electrodes of the storage battery.

[0015] According to the present invention, since a removal signal is generated using current drawn from a power source different from the storage battery, by-product deposits can be removed without consuming the power of the storage battery. [Effects of the Invention]

[0016] Thus, according to the present invention, it is possible to further enhance the effect of preventing and removing the by-product deposits generated on the electrodes of the storage battery, and by being always attached, it is possible to maintain the new state or remove the deposits to a state as close to new as possible, thereby providing a system and a by-product deposit removing device. In addition, since current is drawn from a power source different from the storage battery, the power consumption of the storage battery can be suppressed.

Brief Description of the Drawings

[0017] [Figure 1] FIG. 1 is a functional block diagram showing the circuit configuration of the system according to an embodiment of the present invention. [Figure 2] FIG. 2 is an overall view of the current waveform diagram of the removal signal for the by-product deposits output to the electrodes of the storage battery. [Figure 3] FIG. 3 is an enlarged view of the single pulse current waveform of the current waveform diagram of the removal signal for the by-product deposits output to the electrodes of the storage battery. [Figure 4] FIG. 4 is a functional block diagram showing the circuit configuration of the by-product deposit removing device according to a reference configuration. [Figure 5] FIG. 5 shows the internal resistance value among the graphs showing the transition of the electrical characteristics of the lead storage battery according to Reference Example 1. [Figure 6] FIG. 6 shows the CCA value among the graphs showing the transition of the electrical characteristics of the lead storage battery according to Reference Example 1. [Figure 7] FIG. 7 shows the internal resistance value among the graphs showing the transition of the electrical characteristics of the lead storage battery according to Reference Example 2. [Figure 8] FIG. 8 shows the CCA value among the graphs showing the transition of the electrical characteristics of the lead storage battery according to Reference Example 2. [Figure 9] FIG. 9 is a functional block diagram showing the circuit configuration of the system according to a modification of the present invention.

Embodiments for Carrying Out the Invention

[0018] Preferred embodiments of the present invention will be described in detail below with reference to the attached drawings. Note that the following description pertains only to one aspect of the present invention and does not limit its scope.

[0019] Figure 1 is a functional block diagram showing the circuit configuration of System 1 according to an embodiment of the present invention.

[0020] As shown in Figure 1, the system 1 according to this embodiment includes an external charger 20 capable of charging the storage battery 30 and a by-product deposit removal device 10 that removes by-product deposits generated on the electrodes of the storage battery 30.

[0021] The external charger 20 may be configured to be connected to an external power source 21, such as a commercial power supply or a generator, and to receive power from it. The external charger 20 and the external power source 21 are each examples of power sources different from the storage battery 30. The first function of the external charger 20 is to charge the storage battery 30. The second function of the external charger 20 is to supply power to the by-product sediment removal device 10 for generating a removal signal. The configurations related to each function will be described later.

[0022] The current flowing between the external charger 20 and the external power supply 21, between the external charger 20 and the by-product deposit removal device 10, and between the external charger 20 and the storage battery 30 may be either alternating current or direct current. Depending on whether the current flowing between the external charger 20, the external power supply 21, the by-product deposit removal device 10, and the storage battery 30 is alternating current or direct current, AC / DC converters, DC / AC converters, DC / DC converters, AC / AC converters, etc., may be provided inside or between these components. For example, when the external charger 20 outputs direct current, its output voltage is set according to the rated voltage of the storage battery 30, for example, 12V to 48V.

[0023] In this embodiment, the external charger 20 and external power supply 21 are described as having different configurations as an example, but the system is not limited to this, and system 1 may have a single power supply that has the functions of both the external charger 20 and the external power supply 21.

[0024] The storage battery 30 is, for example, a lead-acid battery, and in this case, the by-product deposit is a lead sulfate film that forms on the negative electrode of the lead-acid battery. The storage battery 30 is not limited to a lead-acid battery, but may also be a nickel-metal hydride battery or a lithium-ion battery, and can be applied to various secondary batteries in which by-product deposits are generated on the electrodes through repeated use.

[0025] The by-product sediment removal device 10 is used by being connected between the external charger 20 and the storage battery 30 (in parallel with the current line for charging from the external charger 20 to the storage battery 30). The by-product sediment removal device 10 comprises an internal power supply 11, a removal signal generation unit 12 that generates a removal signal for removing by-product sediments, and storage battery connection terminals 10A and 10B.

[0026] Battery connection terminal 10A is connected to the positive electrode 31A of the battery 30 via the power cable 19A, and battery connection terminal 10B is connected to the negative electrode 31B of the battery 30 via the power cable 19B. Battery connection terminals 10A and 10B constitute electrode connection parts for connecting the rejection signal generation unit 12 to the positive electrode 31A and negative electrode 31B of the battery 30, respectively.

[0027] The external charger 20 and the internal power supply 11 of the by-product deposit removal device 10 are connected by a current line La1. Power supplied from the external charger 20 is supplied to the internal power supply 11 via the current line La1. This allows the by-product deposit removal device 10 to receive the current necessary to generate the removal signal.

[0028] Furthermore, the external charger 20 and the battery 30 are connected by a current line La2. Power supplied from the external charger 20 is supplied to the battery 30 via the current line La2. This allows the external charger 20 to charge the battery 30.

[0029] The internal power supply 11 uses the current received from the external charger 20 to generate power to operate the rejection signal generation unit 12. For example, if the external charger 20 is an AC power source, the internal power supply 11 may include an AC / DC converter to convert the AC power to DC power. Also, if the external charger 20 outputs DC power, the internal power supply 11 may include a DC / DC converter to step down the output voltage of the external charger 20.

[0030] The rejection signal generation unit 12 includes a drive signal generation unit 13, a switching circuit 17 that performs switching operations according to the drive signal output from the drive signal generation unit 13, and a drive resistor R1 for adjusting the current flowing through the switching circuit 17 to a predetermined value. The battery connection terminal 10A is connected to the battery connection terminal 10B via a current line Lb in which the drive resistor R1 and the switching circuit 17 are inserted in series, and the battery connection terminal 10B is signal-grounded.

[0031] The drive signal generation unit 13 includes a pulse generation circuit 14 that generates a pulse signal and a waveform shaping circuit 15 that shapes the waveform of the pulse signal, and the switching circuit 17 performs switching operations based on the pulse signal after waveform shaping.

[0032] The pulse generation circuit 14 is a circuit that generates a drive signal to drive the switching circuit 17, and is equipped with an oscillator internally, outputting a square wave pulse signal with a predetermined pulse width at a predetermined period. The pulse generation circuit 14 according to this embodiment generates a square wave pulse signal with a pulse width of 300 nsec or more and a pulse period of 20 to 200 μsec. This pulse period corresponds to a frequency of 5 kHz to 50 kHz. The lower limit of the frequency of the rejection signal is not limited to 5 kHz, but may be 7 kHz, 10 kHz, 15 kHz, or 20 kHz. Also, the upper limit of the frequency of the rejection signal is not limited to 50 kHz, but may be 45 kHz, 40 kHz, 35 kHz, 30 kHz, or 25 kHz. Preferred frequency ranges for the rejection signal include 5kHz~50kHz, 5kHz~40kHz, 5kHz~30kHz, 10kHz~50kHz, 10kHz~40kHz, 10kHz~30kHz, 15kHz~50kHz, 15kHz~40kHz, 15kHz~30kHz, 20kHz~50kHz, 20kHz~40kHz, or 20kHz~30kHz. In this embodiment, the notation "first value ~ second value" means a value greater than or equal to the first value and less than or equal to the second value.

[0033] The waveform shaping circuit 15 shapes the square wave pulse signal generated by the pulse generation circuit 14 into a sawtooth wave and outputs it. In other words, the waveform shaping circuit 15 outputs a pulse wave with a gentle rise and a steep fall as the drive signal. By making the rise of the pulse wave gentle in this way, the sudden increase in the current value that flows when the switching circuit 17 is turned on can be suppressed. In addition, by making the fall of the pulse wave steep, the switching operation of the switching circuit 17, which operates using the falling edge as a trigger, can be executed quickly.

[0034] The pulse period of the drive signal should be between 20 and 200 μsec. Furthermore, the pulse width of the drive signal is not limited to 300 nsec, but can be between 300 and 1500 nsec.

[0035] The drive resistor R1 is used to adjust the current value flowing through the current line Lb, and its resistance value is selected so that the maximum pulse current is, for example, 3mA to 2A. The lower limit of the rejection signal current is not limited to 3mA, but may be 5mA, 10mA, 30mA, 50mA, or 100mA. The upper limit of the rejection signal current is not limited to 2A, but may be 1.5A, 1A, 500mA, 300mA, or 200mA. Preferred ranges for the rejection signal current include 3mA to 2A, 3mA to 1A, 3mA to 500mA, 3mA to 300mA, 10mA to 2A, 10mA to 1A, 10mA to 500mA, 10mA to 300mA, 50mA to 2A, 50mA to 1A, 50mA to 500mA, 100mA to 2A, 100mA to 1A, or 100mA to 500mA. In this embodiment, the rejection signal is generated by drawing current from the external charger 20, so the power of the storage battery 30 is not consumed. Therefore, the rejection signal can be output at a lower current value than in the conventional method, and power consumption can be significantly reduced. The maximum value of the pulse current may be 300mA or more. The resistance value of the drive resistor R1 can be determined according to the rated voltage of the storage battery 30 and the input resistance value of the internal power supply 11.

[0036] The switching circuit 17 includes a switching element such as a MOSFET and performs switching operations according to the sawtooth wave pulse signal output from the waveform shaping circuit 15. When the switching circuit 17 is ON, it draws current from the external charger 20, and when the switching circuit 17 is OFF, it stops drawing current from the external charger 20. As a result, a by-product deposit removal signal consisting of a sawtooth wave pulse current, as shown in Figures 2 and 3, is generated and output to the electrodes of the storage battery 30. The pulse period T0 of the removal signal is equal to the pulse period of the drive signal, and the pulse width T1 of the removal signal is approximately equal to the pulse width of the drive signal, although there is a slight deviation due to the influence of the switching element.

[0037] In this way, the by-product deposit removal device 10 can extract a pulsed current from the external charger 20 in accordance with the drive signal output by the drive signal generation unit 13. That is, when the switching circuit 17 is turned on in accordance with the drive signal, a current whose peak value is limited by the drive resistor R1 is extracted from the external charger 20, and this current flows to ground through the current line Lb and the switching circuit 17. Also, when the switching circuit 17 is turned off in accordance with the drive signal, the flow of current from the external charger 20 to ground stops. As a result, the sawtooth wave pulsed current shown in Figures 2 and 3 is generated as a removal signal and output to the electrodes of the storage battery 30.

[0038] Furthermore, when the switching circuit 17 turns off in response to the falling edge of the drive signal, and stops drawing current from the external charger 20, a back electromotive force is generated due to the inductance component including the positive terminal power cable 19A, the negative terminal power cable 19B, and the battery 30, causing a spike-shaped reverse current to flow. This reverse current acts on the negative terminal 31B of the battery 30, removing by-products deposited on the negative terminal 31B of the battery 30.

[0039] In this embodiment, the drive signal input to the switching circuit 17 is a sawtooth wave, and because the rise time of the pulse is gradual, the current value drawn from the external charger 20 also increases gradually, but when the device is turned off, it instantly switches to the off state. Therefore, a sawtooth wave pulse current with a stable peak value can be obtained. In addition, the steep fall from the peak of the sawtooth wave can generate a spike-shaped reverse current (undershoot) with a high peak and narrow pulse width, allowing a current in the opposite direction to the discharge current to be applied to the negative electrode 31B of the battery 30. As will be described in detail later, the peak value of the spike-shaped reverse current is preferably 0.2 to 1.0 times the peak value of the forward sawtooth wave pulse current.

[0040] The spike-like reverse current acts on the negative electrode 31B of the battery 30, causing the by-product deposits (lead sulfate film in lead-acid batteries) deposited on the negative electrode 31B of the battery 30 to peel off and separate at a molecular level. As a result, the area of ​​the electrode surface that was covered by the by-product deposits and is involved in charging is restored to its initial area. In the case of lead-acid batteries, the molecular lead sulfate crystals in the electrolyte separated from the electrode are decomposed during charging into lead ions and sulfate ions. Furthermore, during charging, the generation of H2O, which is produced during the discharge of a lead-acid battery, is also stopped, and as a result, the specific gravity of the electrolyte is improved.

[0041] As shown in Figure 3, when H1 is the amplitude value of the rising edge portion of the single pulse current waveform of the rejection signal, and H2 is the amplitude value of the undershoot after the falling edge of the pulse current waveform, H2 is preferably 0.2 to 1.0 times H1, and more preferably 0.3 to 0.9 times.

[0042] H1 is the amplitude value of the sawtooth wave from the zero-crossing point to the rising peak value, and H2 is the amplitude value of the underpulse from the zero-crossing point to the undershoot peak value. If H2 is less than 0.2 times H1, the effect on by-product deposits is weak, and almost no effect on removing by-product deposits is obtained. Also, if H2 is greater than 1.0 times H1, the underpulse may act not only on the surface of the electrodes of the battery 30 but also inside, potentially damaging the electrodes. By setting H2 to 0.2 times to 1.0 times H1, the spike-like reverse current acts only on the by-product deposits covering the electrode surface, thus reducing the by-product deposits without damaging the electrodes. Therefore, by-product deposits can be effectively removed.

[0043] As described above, the amplitude value H1 of the rising edge (sawtooth wave) of a single pulsed current waveform is preferably, for example, 3mA to 2A, and particularly preferably 300mA or more within that range. If H1 is too small, it will take a long time to remove the by-product deposits, and the by-product deposits will not be effectively removed. When H1 is, for example, 300mA, which is an appropriate pulsed current, it is possible to generate a moderately sized spike-shaped reverse current (underpulse) without damaging the electrodes, thereby enhancing the removal effect of by-product deposits.

[0044] When T1 is the rise time width of a single pulse current waveform and T2 is the fall time width accompanied by undershoot, it is preferable that T2 is 0.02 to 0.2 times T1. If T2 is smaller than 0.02 times T1, T2 becomes excessively small compared to T1, causing the undershoot amplitude H2 to become excessively large, which makes the electrodes more susceptible to damage. Alternatively, if T1 becomes excessively large compared to T2, power consumption increases. Furthermore, the heat generated due to power consumption may reduce the effectiveness of removing by-product deposits.

[0045] Furthermore, if T2 is greater than 0.2 times T1, T2 becomes excessively large compared to T1, causing the undershoot amplitude H2 to become excessively small, resulting in no removal effect of by-product deposits. Alternatively, if T1 becomes excessively small compared to T2, the charge charge to the capacitor for generating the sawtooth wave becomes insufficient, causing the undershoot amplitude H2 to become excessively small, and thus no removal effect of by-product deposits. By setting T2 to 0.02 to 0.2 times T1, a large undershoot can be generated to effectively remove by-product deposits adhering to the surface of the electrodes of the battery 30.

[0046] The pulse current waveform of the removal signal preferably includes a ringing waveform following an undershoot. The ringing imparts micro-vibrations to the by-product deposits, promoting the redissolution (reduction) of by-products into the electrolyte. It also has a preventative effect of suppressing the adhesion (crystallization) of by-products. The time width T3 of the ringing waveform is preferably 100 nsec or more, and particularly preferably 200 nsec or more. For example, in lithium-ion batteries, using a pulse that includes a ringing waveform can particularly enhance the effect of redissolution (reduction) of by-products.

[0047] T1 is approximately equal to the pulse width of the drive signal (e.g., 300 nsec). T2 is 300 nsec or less, preferably between 5 nsec and 300 nsec. The steep falling edge of the pulse current waveform of the removal signal can generate not only undershoot but also ringing, and the ringing effect can further enhance the removal effect of by-product deposits.

[0048] If the storage battery 30 is, for example, a lead-acid battery, a lead sulfate film, which is a by-product deposit, will form on its negative electrode. In this embodiment, a nanopulse current in the opposite direction to the discharge direction (charging direction) can be generated by utilizing the forward (discharge direction) current taken from the external charger 20, and this can be applied to the negative electrode 31B of the storage battery 30. Therefore, the by-products deposited on the negative electrode 31B of the storage battery 30 can be removed by electrolysis, and the by-product deposits can be efficiently removed without damaging the electrode.

[0049] In system 1 according to this embodiment, while the external charger 20 is charging the storage battery 30, the removal signal generation unit 12 generates a removal signal using the current drawn from the external charger 20. This allows for the removal of by-product deposits in parallel with the charging of the storage battery 30.

[0050] Furthermore, in System 1 according to this embodiment, even when the battery 30 has been fully charged by the external charger 20, the removal signal generation unit 12 can continue to generate a removal signal using the current drawn from the external charger 20. For example, in a battery management system (BMS) using a lithium-ion battery, the supply of current to the battery may be stopped once charging is complete. However, in this embodiment, by continuing to supply power from the external charger 20 to the by-product deposit removal device 10, the removal signal can continue to be applied even after charging is complete. This makes it possible to continuously remove by-product deposits, for example, 24 hours a day, 365 days a year, and maintain the battery 30's capacity as it was when new.

[0051] As described above, the system 1 according to this embodiment includes an external charger 20 capable of charging a storage battery 30 and a by-product deposit removal device 10 for removing by-product deposits generated on the electrodes of the storage battery 30. The by-product deposit removal device 10 includes a removal signal generation unit 12 that generates a by-product deposit removal signal using current taken from the external charger 20. The removal signal consists of a periodic pulse current, and when the amplitude value of the rising portion of a single pulse current waveform of the removal signal is H1, and the amplitude value of the undershoot after the falling of the pulse current waveform is H2, then H2 is 0.2 to 1.0 times H1, and when the time width of the rising portion of the pulse current waveform is T1, and the time width of the falling portion accompanied by the undershoot is T2, then T2 is 0.02 to 0.2 times T1. Therefore, by-product deposits adhering to the surface of the electrodes can be efficiently removed without damaging the electrodes of the storage battery. Furthermore, since current is drawn from the external charger 20, by-product deposits can be continuously removed without consuming power from the storage battery 30.

[0052] The following describes a reference example conducted to confirm the effectiveness of the by-product sediment removal signal. In the following reference example, the experiment was conducted using the reference configuration shown in Figure 4.

[0053] Figure 4 is a functional block diagram showing the circuit configuration of a by-product sediment removal device 10' according to a reference configuration. The reference configuration shown in Figure 4 differs from system 1 according to this embodiment in that it draws current for generating a removal signal from a storage battery 30. Specifically, the by-product sediment removal device 10' according to the reference configuration is used by connecting it to a pair of electrodes of a storage battery 30, and comprises storage battery connection terminals 10A and 10B, a power supply unit 11', and a removal signal generation unit 12 that generates a removal signal for removing by-product sediments. Storage battery connection terminal 10A is connected to the positive electrode 31A of the storage battery 30 via a power cable 19A, and storage battery connection terminal 10B is connected to the negative electrode 31B of the storage battery 30 via a power cable 19B. The power supply unit 11' is connected to the storage battery connection terminal 10A via a current line Lc, and includes a DC / DC converter for stepping down the output voltage of the storage battery 30, and operates the removal signal generation unit 12 using the current drawn from the storage battery 30. The rejection signal generation unit 12 and the battery connection terminal 10A are connected via a current line Ld. The rejection signal generation unit 12 has the same configuration as the rejection signal generation unit 12 of this embodiment and generates a rejection signal having the same waveform characteristics.

[0054] In the following reference example, the effect of removing by-product sediments was confirmed using the reference configuration shown in Figure 4. Since System 1 according to this embodiment also applies a removal signal having the same waveform characteristics as the reference configuration to the electrodes of the storage battery 30, the same by-product sediment removal effect as in the following reference example can be obtained.

[0055] (Example 1: Degradation & Recovery Report of Carbon-Containing Pb Electrodes) A new lead-acid battery (12V battery) containing carbon in its electrode material was prepared and installed in a vehicle for use. As mentioned above, carbon in Pb electrodes is known to have an effect in suppressing sulfation. Before starting to use this new lead-acid battery, its electrical characteristics were measured, including internal resistance, CCA (Cold Cranking Ampere) value, and electrolyte specific gravity. For the specific gravity, the specific gravity of the electrolyte in each of the six cells constituting the 12V battery was measured using a hydrometer, and the average value was calculated. As a result, as shown in Table 1, the internal resistance of the battery (BT) was 6.45 mΩ, the CCA value was 381, and the specific gravity of the electrolyte (average value) was 1.268.

[0056] Four years after the start of use of the lead-acid battery, the car dealer told the customer that it was time to replace the battery at each statutory inspection, but the customer continued to use it without replacing it. Subsequently, 5 years and 7 days after the start of use of the lead-acid battery, a by-product deposit removal device (this device) with the reference configuration shown in Figure 4 was installed and a recovery test was started. At that time, the electrical characteristics of the lead-acid battery were checked in advance. In the evaluation of electrical characteristics, the capacity of the storage battery was also included. For the capacity measurement, the discharge current was 6.0A (30Ah, 5-hour rate), the termination voltage was 10.5V, and the starting condition was immediately after full charge. As a result, the internal resistance value was 14.35mΩ, the CCA value was 171, the specific gravity of the electrolyte (average value) was 1.197, the measured capacity was 206.916Wh (17.960Ah), and the discharge time was 2 hours 57 minutes 10 seconds. In this way, it was confirmed that the lead-acid battery was actually in a deteriorated state.

[0057] Twenty-three days after the start of the recovery test, the recovery status of the lead-acid battery was checked. The internal resistance was 8.43 mΩ, the CCA value was 292, the specific gravity of the electrolyte (average value) was 1.239, the measured capacity was 235.878 Wh (20.474 Ah), and the discharge time was 3 hours, 21 minutes, and 50 seconds. Thus, it was confirmed that the battery characteristics had entered the recovery range.

[0058] The recovery test was continued, and 1 year and 309 days after the start of the recovery test, the recovery status of the lead-acid battery was checked. The internal resistance was 6.75 mΩ, the CCA value was 364, the specific gravity of the electrolyte (average value) was 1.268, the measured capacity was 330.030 Wh (28.644 Ah), and the discharge time was 4 hours, 46 minutes, and 44 seconds. The changes in the internal resistance and CCA values ​​are shown in Figures 5 and 6, respectively. Thus, it was confirmed that the battery characteristics were fully recovered by continuing to use this device.

[0059] [Table 1] From the above results, it was confirmed that by using this device, the degradation of lead-acid batteries due to sulfation, which cannot be prevented even when carbon-containing Pb electrode material is used, can be sufficiently restored. System 1 according to this embodiment also generates a removal signal with similar waveform characteristics, and therefore a similar restoration effect can be obtained.

[0060] (Reference example 2: Recovery experiment using additive (surfactant) injection) To restore a lead-acid battery (12V battery) for automobiles that had deteriorated due to long-term use, a recovery test was conducted in which an additive (surfactant) was injected into the electrolyte to allow continued use. At the start of the recovery test, the electrical characteristics of the lead-acid battery were measured as follows: internal resistance, CCA (Cold Cranking Ampere) value, specific gravity of the electrolyte, and capacity. As shown in Table 2, the internal resistance of the battery (BT) was 8.93 mΩ, the CCA value was 288, the specific gravity of the electrolyte (average value) was 1.222, the measured capacity was 208.757 Wh (18.120 Ah), and the discharge time was 2 hours, 56 minutes, and 41 seconds.

[0061] The recovery status of the lead-acid battery was checked 33 days after the start of the test. The results showed an internal resistance of 8.11 mΩ, a CCA value of 294, an average specific gravity of the electrolyte of 1.230, a measured capacity of 232.030 Wh (20.140 Ah), and a discharge time of 3 hours, 11 minutes, and 03 seconds. Thus, a slight recovery in the battery characteristics was observed.

[0062] Recovery tests were continued, and the recovery status of the lead-acid battery was checked 40 days after the start of the tests. The results showed an internal resistance of 7.88 mΩ, a CCA value of 312, an average specific gravity of the electrolyte of 1.238, a measured capacity of 266.334 Wh (23.118 Ah), and a discharge time of 3 hours, 35 minutes, and 44 seconds.

[0063] Furthermore, 56 days after the start of the test, the internal resistance was 7.99 mΩ, the CCA value was 306, the specific gravity of the electrolyte (average value) was 1.233, the measured capacity was 239.998 Wh (20.832 Ah), and the discharge time was 3 hours, 17 minutes, and 17 seconds. Thus, although the battery characteristics gradually recovered over approximately three months, a saturation trend in the values ​​was observed, and no significant recovery was seen.

[0064] Therefore, the by-product deposit removal device (the device shown) with the reference configuration shown in Figure 4 was attached to the lead-acid battery, and the recovery test was continued. The recovery status of the lead-acid battery was checked 14 days after the attachment of the device. As a result, the internal resistance was 6.87 mΩ, the CCA value was 358, the specific gravity of the electrolyte (average value) was 1.238, the measured capacity was 311.791 Wh (27.063 Ah), and the discharge time was 4 hours, 31 minutes, and 11 seconds. The changes in the internal resistance and CCA values ​​are shown in Figures 7 and 8, respectively. In this way, by using the by-product deposit removal device, the battery characteristics recovered rapidly, and good results were obtained.

[0065] [Table 2]

[0066] From the above results, it was confirmed that by using this device, the degradation of lead-acid batteries due to sulfation, which cannot be prevented even with the use of additives (surfactants), can be sufficiently restored. System 1 according to this embodiment also generates a removal signal with similar waveform characteristics, and therefore a similar restoration effect can be obtained.

[0067] (Reference Example 3: Recovery experiment of laminated lithium-ion battery) A recovery experiment was conducted using a by-product deposit removal device (the device shown in Figure 4) with the reference configuration shown, applied to a laminate-type lithium-ion battery. In the recovery experiment, lithium-ion battery samples No. 1 to No. 3 were prepared, and the lithium-ion batteries were charged and discharged with the device attached in an attempt to restore their performance.

[0068] During the charging of the lithium-ion battery, constant current constant voltage (CCCV) mode was applied, and constant current charging was performed at a charging current of 0.2 ItA until the voltage reached 4.2V. After the charging voltage reached 4.2V, charging continued at a constant voltage of 4.2V, and charging was terminated when the charging current reached 0.01 ItA. After a 30-minute pause in charging, the lithium-ion battery was discharged. During discharge, constant current mode (CC) was applied, and constant current discharge was performed at a discharge current of 0.2 ItA until the discharge voltage reached 2.75V.

[0069] The above charge → pause charge → discharge cycle was defined as one charge-discharge operation, and the device was operated while repeating the charge-discharge operation for a predetermined number of cycles. In this way, recovery experiments were conducted on lithium-ion battery samples No. 1, No. 2, and No. 3, and the capacity of the lithium-ion batteries before and after the recovery experiment was measured at a public testing institution. The capacity measurement was performed in a 25°C forced-air constant temperature chamber after discharge and full charge under the same conditions. The results are shown in Table 3.

[0070] [Table 3]

[0071] Lithium-ion battery sample No. 1 has a nominal capacity of 1400mAh, but its capacity before attaching this device was 1196mAh. After performing 215 charge-discharge cycles with this device attached, the capacity was remeasured and measured at 1255mAh, resulting in a capacity increase of 4.70%.

[0072] Lithium-ion battery sample No. 2 also has a nominal capacity of 1400mAh, but its capacity before attaching this device was 968mAh. After performing 215 charge-discharge cycles with this device attached, the capacity was remeasured and found to be 1055mAh, resulting in a capacity increase of 8.25%. Thus, although sample No. 2 was more degraded than sample No. 1, it recovered in a similar manner to sample No. 1, and in particular, showed a higher capacity increase than sample No. 1.

[0073] Lithium-ion battery sample No. 3 has a nominal capacity of 2500mAh, but its capacity before the installation of this device was 2491mAh. After 410 charge-discharge cycles with the device installed, the capacity was remeasured and found to be 2566mAh, representing a capacity increase of 2.92%. Thus, although sample No. 3 showed little degradation, the application of this device restored its capacity, resulting in a good result that exceeded the nominal capacity.

[0074] From the above results, it was confirmed that this device has a recovery effect on the degradation of lithium-ion batteries. System 1 according to this embodiment also generates a removal signal with similar waveform characteristics, and therefore a similar recovery effect can be obtained. Accordingly, the system and by-product deposit removal device of the present invention enable the reuse of degraded batteries and contribute to the reduction of discarded batteries and CO2 emissions.

[0075] Although preferred embodiments of the present invention have been described above, it goes without saying that the present invention is not limited to the above embodiments, and various modifications are possible without departing from the spirit of the invention, and these modifications are also included within the scope of the present invention. System 1 may, for example, charge a mobile terminal equipped with a battery (e.g., a smartphone and a personal computer, etc.) while restoring the capacity of the battery. That is, in one embodiment, System 1 may have aspects of a charger and battery recovery device for such a mobile terminal.

[0076] For example, the by-product deposit removal device according to the present invention is not limited to the use of removing lead sulfate film generated on the electrodes of lead-acid batteries, but can be applied to various uses of removing by-product deposits generated on the electrodes of batteries by electrolysis.

[0077] Furthermore, as shown in Figure 9, the system 1 according to the present invention may be configured without a function to charge the storage battery 30. The modified system 1 shown in Figure 9 may not have an external charger 20 and may be configured to supply power to the by-product sediment removal device 10 from an external power source 21. In this configuration, the by-product sediment removal device 10 is equipped with storage battery connection terminals 10A and 10B, acquires power from the external power source 21 via the current line La1, and outputs a removal signal to the electrodes of the storage battery 30 via the current line Lb. The external power source 21 is an example of a power source different from the storage battery 30, and may be, for example, an AC / DC adapter that acquires power from a commercial power source or an accessory power source for a vehicle. With this configuration, even when the storage battery 30 is not being charged, power can be acquired from the external power source 21 to generate a removal signal and output to the electrodes of the storage battery 30. [Explanation of Symbols]

[0078] 1 System 10 By-product deposit removal device 10A, 10B Battery Connection Terminals 11 Internal power supply 12 Removal signal generation section 13 Drive signal generation unit 14. Pulse generation circuit 15 Waveform shaping circuit 17 Switching Circuits 30 Storage batteries R1 Drive resistor

Claims

1. A system comprising a power source capable of charging a storage battery, and a by-product deposit removal device for removing by-product deposits generated on the electrodes of the storage battery, The by-product deposit removal apparatus is, A removal signal generation unit that generates a removal signal for the by-product deposits, A rejection signal generation unit comprising a switching circuit, which, when the power supply is charging the battery, causes the current drawn from the power supply to flow to ground by the ON operation of the switching circuit, and uses the back electromotive force generated by the OFF operation of the switching circuit to generate a rejection signal based on a reverse current in the opposite direction to the charging direction of the battery, An electrode connection unit that outputs the removal signal to the electrodes of the storage battery, A system that includes these features.

2. The system according to claim 1, wherein the removal signal generation unit generates the removal signal using the current drawn from the power supply, even when the battery has been fully charged by the power supply.

3. The system according to claim 1, wherein the rejection signal includes a pulsed current having a period of 5 kHz to 50 kHz.

4. The system according to claim 1, wherein the electrode connection part outputs the removal signal with a current of 3 mA to 2 A.

5. The aforementioned rejection signal consists of a periodic pulse current. The amplitude value of the rising edge of the single pulse current waveform of the rejection signal is H １ The amplitude value of the undershoot after the falling edge of the pulse current waveform is H ２ In that case, H ２ H １ It is 0.2 to 1.0 times, The rise time width of the pulse current waveform is T １ Let T be the time width of the fall with the undershoot. ２ In that case, the above T ２ is the aforementioned T １ The system according to claim 1, wherein the value is 0.02 times to 0.2 times.

6. The pulse current waveform includes a ringing waveform following the undershoot, and the time width T of the ringing waveform ３ is ２ 2 to 10 times that of the T, and the system according to claim 5.

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