JP2007220658A - Packed battery, power supply system, and method of manufacturing packed battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a battery pack in which charge and discharge depth can be detected precisely, which is high in reliability and in which a stable high output can be obtained. <P>SOLUTION: This is the battery pack in which a plurality of nonaqueous secondary batteries A12 is made as the main body and in which the plurality of the nonaqueous secondary batteries A and a storage element B13 having at least one piece of nonaqueous electrolyte for voltage detection are connected in series, and when a voltage difference between a voltage (V<SB>A1</SB>) per a unit cell at the discharge depth 25% and the voltage (V<SB>A2</SB>) per the unit cell at the discharge depth 75% in the nonaqueous secondary battery A is made as ΔV<SB>A</SB>, and the voltage (V<SB>B1</SB>) per the unit cell at the discharge depth corresponding to the discharge depth 25% of the nonaqueous secondary battery A and the voltage (V<SB>B2</SB>) per the unit cell at the discharge depth corresponding to the discharge depth 75% of the nonaqueous secondary battery A in the storage element B is made as ΔV<SB>B</SB>, the ΔV<SB>B</SB>of the storage element B is larger than the ΔV<SB>A</SB>of the nonaqueous secondary battery A. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an assembled battery in which a plurality of batteries are configured in series, a power supply system using the assembled battery, and an assembled battery manufacturing method.

  In recent years, a large power supply system used in an electric vehicle, a hybrid electric vehicle, a home, or the like uses an assembled battery in which a plurality of batteries are connected in order to obtain a desired output. Non-aqueous secondary batteries, such as lithium ion secondary batteries and lithium polymer secondary batteries, are attracting attention as batteries for large power supply systems because of their light weight, high capacity, and high output.

  A battery that can be used in a wide range of charge / discharge depths is preferable as the battery used for the large power supply system as described above, and it is not preferable that the output greatly fluctuates in order to obtain stable power. Since the battery output is (battery voltage) × (current) or (voltage) × (voltage) ÷ (battery internal resistance), it greatly depends on the battery voltage or the battery internal resistance. In general, a non-aqueous secondary battery such as a lithium ion secondary battery has a high battery voltage and a low internal resistance when the charge depth is deep or the discharge depth is shallow. Conversely, when the charging depth is shallow or the discharging depth is deep, the battery voltage tends to be low and the internal resistance of the battery tends to increase. Therefore, by reducing the difference in the battery voltage depending on the charge / discharge depth or the difference in the internal resistance of the battery depending on the charge / discharge depth, fluctuations in output can be reduced even when used over a wide range of charge / discharge depths.

  When multiple non-aqueous secondary batteries are connected and used as an assembled battery, a discharge reserve is ensured to prevent over-discharge of single cells with small capacity due to variations in the capacity of each single cell during discharge. In order to avoid deterioration of the battery due to a phase change or the like of the positive electrode active material due to a high voltage during charging, an intermediate charge / discharge depth is used. For example, in a general-purpose lithium ion secondary battery using cobalt-based oxide as the positive electrode active material and graphite as the negative electrode active material, avoid use in the upper and lower limit regions of the charge / discharge depth, and usually about 25 The range of the charge / discharge depth (25 to 75%) excluding around% is used.

  As a method for detecting the charge / discharge depth of the secondary battery as described above, a method utilizing the temperature of the battery, integration of the current value, or the like is known. However, since these methods are likely to cause errors in long-term use, detection is also performed from the voltage of the battery or the internal resistance of the battery. Here, the internal resistance can be obtained from the equation [internal resistance = ΔV / ΔI] from the current value change ΔI flowing through the battery and the battery voltage change ΔV at that time.

When the charge / discharge depth is detected from the battery voltage or the internal resistance of the battery, the battery voltage or the internal resistance of the battery is increased according to the charge / discharge depth in the region of the charge / discharge depth, as opposed to reducing the output fluctuation. It is preferable to change. However, when a non-aqueous secondary battery having a flat voltage change or internal resistance change is used, it is difficult to detect the charge / discharge depth based on the battery voltage or the internal resistance of the battery. In particular, LiNi _0.5 Mn _1.5 O ₄ , which is a 5 V class spinel type lithium manganese oxide, and non-aqueous secondary batteries in which an iron phosphate compound is used as a positive electrode active material are much more difficult than conventional positive electrode active materials. The battery has a flat charge / discharge curve and is expected as a battery with small output fluctuation. Therefore, an assembled battery composed of a non-aqueous secondary battery having such a positive electrode active material has a small output fluctuation at a wide range of charge / discharge depth and excellent stability, but it is based on voltage detection or internal resistance detection of the battery. It becomes difficult to detect the charge / discharge depth by the method.

  In general, when non-aqueous secondary batteries are used up to shallow or deep charge / discharge depths, it is easy to detect voltage or internal resistance of the battery. It is not done. Furthermore, in an assembled battery composed of a plurality of batteries, there is a difference in capacity for each unit cell, so that some batteries are likely to be overcharged or overdischarged. For this reason, it is not preferable to use it up to a shallow or deep region of charge / discharge depth. Although it is conceivable to arrange the detection circuit separately so that the voltage or the internal resistance of the battery is accurately detected for each battery of the assembled battery, the device becomes complicated and a high-precision detection element is required. There is a problem that increases.

  Then, several methods are proposed about the case where the above several non-aqueous secondary batteries are connected and used as an assembled battery. For example, Patent Document 1 proposes a method using an assembled battery in which an aqueous secondary battery such as a nickel hydrogen battery having a smaller capacity than a nonaqueous secondary battery and having a smaller capacity than the nonaqueous secondary battery is connected. . According to this assembled battery, since the end of charging is detected by the aqueous secondary battery having a small capacity, the charging is terminated before the non-aqueous secondary battery is overcharged. Further, since the aqueous secondary battery exhibits a unique voltage behavior different from that of the non-aqueous secondary battery at the end of charging, the charging depth of the entire assembled battery can be detected by detecting the voltage of only the aqueous secondary battery.

Further, depending on how the battery is used, it may be difficult to detect the charge / discharge depth with the battery voltage. For example, when the battery is always used and a current flows, the voltage fluctuates depending on the magnitude of the current, so that the battery voltage may not match the charge / discharge depth. For example, Patent Document 2 proposes a method of measuring current and voltage, measuring the internal resistance of the battery from the measured values, and associating the internal resistance of the battery with the charge / discharge depth.
JP-A-9-180768 JP 2000-21455 A

  However, the assembled battery disclosed in Patent Document 1 has a problem that the relationship between the charge / discharge depth and the voltage at the time of setting shifts as it is used.

  That is, in the method based on voltage detection in Patent Document 1, since a large voltage change at the time of full charge in an aqueous secondary battery is a measurement target, it is easy to detect the end of charge. However, in an aqueous solution type secondary battery, even if a charging current flows in the overcharge region, the current is not used for charging and water in the electrolyte is electrolyzed. Even when the battery is in the overcharge region, the non-aqueous secondary battery does not reach full charge, and charging is continued. Moreover, in the case of an aqueous solution type secondary battery, a part of the charging current is not used for charging but used for electrolysis of water when a large charging current flows even in a normal use region or when the environmental temperature is high. . Therefore, even when the battery pack is manufactured so that the uncharged state of the aqueous secondary battery and the non-charged state of the non-aqueous secondary battery are set to coincide with each other, the charge / discharge depth of the aqueous secondary battery is relatively easy. The relationship between the charge / discharge depth of the non-aqueous secondary battery shifts. In particular, since the assembled battery of Patent Document 1 has a capacity of an aqueous secondary battery smaller than that of a non-aqueous secondary battery, the aqueous secondary battery always has an overcharge region that causes capacity deterioration. The battery is charged, and the charge / discharge depth shifts due to this capacity deterioration. For this reason, there is a problem that the function of controlling charging / discharging of the entire assembled battery by predicting the charging state of the non-aqueous secondary battery by using the voltage drop at the time of full charge of the aqueous secondary battery is lost. .

Moreover, in the method of associating the internal resistance of the battery with the charge / discharge depth disclosed in Patent Document 2, detection is easy in the case of a battery having a large internal resistance. However, when a non-aqueous secondary battery having a very small change in internal resistance of the battery, which is preferable as a power supply for the power supply system, is used, it is difficult to detect the charge / discharge depth by the internal resistance. In particular, in a non-aqueous secondary battery in which LiNi _0.5 Mn _1.5 O ₄ which is a 5 V class spinel type lithium manganese oxide or an iron phosphate compound is used as a positive electrode active material, a conventional nickel oxide or cobalt oxide is used. Compared to non-aqueous secondary batteries using a positive electrode active material such as the above, since the change in internal resistance due to the depth of charge and discharge is small, it is difficult to detect the depth of charge and discharge with the method based on the internal resistance detection of the battery. is there.

  The present invention has been made in view of the above problems, and can provide a stable high output and increase the complexity of a device when an assembled battery mainly including a plurality of nonaqueous secondary batteries is used in a large power supply system. It is an object of the present invention to provide a highly reliable assembled battery which can effectively detect overcharge and overdischarge by accurately detecting the charge / discharge depth of the assembled battery without incurring the problem.

The assembled battery of the present invention that has solved the above problems is a power storage element B mainly composed of a plurality of non-aqueous secondary batteries A and having the plurality of non-aqueous secondary batteries A and at least one non-aqueous electrolyte for voltage detection. Are connected in series, and the non-aqueous secondary battery A has a voltage per unit cell at a discharge depth of 25% (V _A1 ) and a voltage per unit cell at a discharge depth of 75% (V _A2 ) is defined as ΔV _A, and the voltage per unit cell (V _B1 ) at the discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A in the electricity storage element B and the non-aqueous two when the voltage difference between the voltage (V _B2) per single cell in the discharge depth corresponding to the depth of discharge of 75% of the next cell a △ and V _B, △ V _B is the non-aqueous secondary of said power storage device B It is greater than △ V _a of the battery a.

  According to the above configuration, the non-aqueous secondary battery A within a discharge depth range corresponding to the flat discharge depth range of the voltage change in the non-aqueous secondary battery A that requires a stable high output for a large power supply system. The battery element B having a voltage change per unit cell larger than the voltage change per unit cell is incorporated into the assembled battery. Since the charging / discharging depth of the assembled battery is detected by the voltage change of the electric storage element B, the accurate charging / discharging depth can be detected as compared with the assembled battery of the non-aqueous secondary battery A alone. Moreover, since the electrical storage element B which has a nonaqueous electrolyte with few deviation | shifts of the charge / discharge depth by charging / discharging is used as a battery for a detection, the shift | offset | difference of the charge / discharge depth from the setting of the electrical storage element B is suppressed also by long-term use. It is done. As a result, the charge / discharge depth of the nonaqueous secondary battery A is prevented from deviating from the detected charge / discharge depth of the assembled battery.

In the present invention, the battery capacity C _B per unit cell of the electricity storage element B is preferably larger than the battery capacity C _A per unit cell of the non-aqueous secondary battery A.

According to the above configuration, since the battery capacity C _B per unit cell of the storage element B is larger than the battery capacity C _A per unit cell of the non-aqueous secondary battery A, the end of charging of the assembled battery is the charge of the storage element B. Not regulated by end of life. Therefore, the high-power nonaqueous secondary battery A constituting the main body of the assembled battery is effectively used.

  In the present invention, the electrical storage element B preferably uses an electric double layer capacitor.

  According to the above configuration, since a power storage element having a large voltage change is obtained, the charge / discharge depth of power storage element B is accurately detected.

  In the present invention, it is preferable to use a non-aqueous secondary battery as the electricity storage element B.

  According to the above configuration, since a non-aqueous secondary battery having a high energy density is used as a storage element for detection, a decrease in energy density of the entire assembled battery can be suppressed. Further, it is possible to obtain the power storage element B in which the relationship between the charge / discharge depth and the voltage is less shifted from the setting time.

  In the present invention, when a non-aqueous secondary battery similar to the non-aqueous secondary battery A is used as the storage element B, the negative electrode of the non-aqueous secondary battery A contains a graphite-based carbon material as a negative electrode active material. The negative electrode of the electricity storage element B preferably contains at least one material selected from amorphous carbon, an alloy, and a metal oxide as a negative electrode active material.

  According to the above configuration, the graphite-based carbon material has a small voltage change in the normal use region of the non-aqueous secondary battery, and the material such as amorphous carbon has a large voltage change in the same region, so that the voltage detection is easy. . In addition, an assembled battery composed of a combination of the non-aqueous secondary battery A and the power storage element B with high output and little deviation in the charge / discharge depth can be obtained.

In the present invention, when a non-aqueous secondary battery similar to the non-aqueous secondary battery A is used as the electricity storage element B, the positive electrode of the non-aqueous secondary battery A has an iron phosphate compound and nickel manganese as the positive electrode active material. The positive electrode of the electricity storage element B contains at least one selected from spinel oxides, and LiMO ₂ (wherein M is selected from the group consisting of Ni, Co, Mn, Al, and Mg). It is preferable to contain a lithium oxide represented by a seed.

According to the above configuration, the iron phosphate compound or nickel manganese spinel oxide as the positive electrode active material has a very small voltage change in the normal use region of the non-aqueous secondary battery, and is represented by LiMO ₂ as the positive electrode active material. Since the voltage change of the lithium oxide is large in the same region, voltage detection is easy. In addition, an assembled battery composed of a combination of the non-aqueous secondary battery A and the power storage element B with high output and little deviation in the charge / discharge depth can be obtained.

Moreover, the assembled battery of the present invention that has solved the above-mentioned problems is mainly composed of a plurality of non-aqueous secondary batteries A, and includes the plurality of non-aqueous secondary batteries A and at least one non-aqueous electrolyte for detecting internal resistance. An assembled battery in which a storage element D is connected in series, and the non-aqueous secondary battery A has an internal resistance (R _A1 ) per unit cell at a discharge depth of 25% and a unit cell at a discharge depth of 75%. the internal resistance of the difference between (R _A2) △ and R _a, internal resistance per cell in the discharge depth corresponding to the depth of discharge of 25% of the non-aqueous secondary battery a in the electric device D (R _D1) wherein when the difference of △ R _D of the internal resistance per cell in the discharge depth corresponding to the depth of discharge of 75% of the non-aqueous secondary battery _{a (R D2), △ R} D of the electric device D is the wherein the larger than △ R _a nonaqueous secondary battery a

  According to the above configuration, in the non-aqueous secondary battery A in a non-aqueous secondary battery A that requires a stable and high output, the non-aqueous secondary battery has a discharge depth range corresponding to the flat discharge depth range of the internal resistance change. A storage element D having an internal resistance change per unit cell larger than the internal resistance change per unit cell of A is incorporated in the assembled battery. Since the charge / discharge depth of the assembled battery is detected by the internal resistance change of the electricity storage element D, it is possible to detect an accurate charge / discharge depth as compared with the assembled battery of the non-aqueous secondary battery A alone.

In the present invention, the battery capacity C _D per unit cell of the electricity storage element D is preferably larger than the battery capacity C _A per unit cell of the non-aqueous secondary battery A.

According to the above configuration, the charging of the battery capacity C _D for the larger cell capacity C _A per unit cell of the non-aqueous secondary battery A, the end of charging power storage device D of the battery pack per unit cell of the storage element D Not regulated by end of life. Therefore, the high-power nonaqueous secondary battery A constituting the main body of the assembled battery is effectively used.

  In the present invention, it is preferable to use a non-aqueous secondary battery as the power storage element D.

  According to the above configuration, since a non-aqueous secondary battery having a high energy density is used as a storage element for detection, a decrease in energy density of the entire assembled battery can be suppressed. In addition, it is possible to obtain the energy storage element D in which the relationship between the charge / discharge depth and the internal resistance of the battery is less deviated from the setting time.

  In the present invention, when a non-aqueous secondary battery similar to the non-aqueous secondary battery A is used as the storage element D, the negative electrode of the non-aqueous secondary battery A contains a graphite-based carbon material as a negative electrode active material. The negative electrode of the electricity storage element D preferably contains at least one material selected from amorphous carbon, an alloy, and a metal oxide as a negative electrode active material.

  According to the above configuration, the graphite-based carbon material has a small change in internal resistance in the normal use region of the non-aqueous secondary battery, and the material such as amorphous carbon has a large change in internal resistance in the same region. Easy. Moreover, the assembled battery which consists of the combination of the non-aqueous secondary battery A and the electrical storage element D with high output and few deviations in the charge / discharge depth is obtained.

In the present invention, when a non-aqueous secondary battery similar to the non-aqueous secondary battery A is used as the electricity storage element D, the positive electrode of the non-aqueous secondary battery A has an iron phosphate compound and nickel manganese as the positive electrode active material. It contains at least one selected from spinel oxides, and the positive electrode of the electricity storage element D has LiMO ₂ as a positive electrode active material (where M is at least one selected from the group consisting of Ni, Co, Mn, Al, and Mg). It is preferable to contain a lithium oxide represented by a seed.

According to the above configuration, the iron phosphate compound or nickel manganese spinel oxide as the positive electrode active material has a very small change in internal resistance in the normal use region of the non-aqueous secondary battery, and LiMO ₂ as the positive electrode active material. Since the lithium oxide represented has a large internal resistance change in the same region, voltage detection is easy. In addition, an assembled battery composed of a combination of the non-aqueous secondary battery A and the power storage element B with high output and little deviation in the charge / discharge depth can be obtained.

  In the present invention, by configuring the power supply system using the assembled battery, a power supply system is provided that has high output regardless of the charge / discharge depth, small output fluctuation, and the charge / discharge depth is accurately controlled. Can do.

In addition, the present invention mainly includes a plurality of non-aqueous secondary batteries A, and a plurality of non-aqueous secondary batteries A and at least one non-aqueous electrolyte for voltage detection are connected in series. cage, then a voltage difference △ V _a and the voltage (V _A2) per single cell in the discharge depth 75% voltage (V _A1) of per cell of the 25% depth of discharge in the non-aqueous secondary battery a , Corresponding to a voltage per unit cell (V _B1 ) at a discharge depth corresponding to a discharge depth of 25% of the non-aqueous secondary battery A in the electricity storage element B and a discharge depth of 75% of the non-aqueous secondary battery A. when the voltage difference between the voltage per unit cell in the discharge depth (V _B2) and △ V _B, △ V _B of the power storage device B is larger than △ V _a nonaqueous secondary battery a, and the battery capacity C _B is the nonaqueous secondary battery of per cell storage element B A method for producing an assembled battery having a battery capacity C _A larger than a battery cell A, wherein the battery element B is precharged before the non-aqueous secondary battery A and the battery element B are connected. It is what.

  In the case of an assembled battery in which the capacity of the storage element B is larger than the capacity of the non-aqueous secondary battery A so that the capacity of the non-aqueous secondary battery A constituting the main body of the assembled battery can be used effectively, for example, the uncharged of both batteries When the initial state is set so that the discharge depth of the state matches, the discharge depth of the electricity storage element B becomes shallower than the discharge depth of the nonaqueous secondary battery at the end of charging of the assembled battery. Therefore, since there is a bias in the charge / discharge depth at the time of charge / discharge in the storage element B, there is a possibility that the storage element B will be discharged until complete discharge, and the battery is likely to deteriorate due to the charge / discharge cycle. Deviation tends to occur in the relationship. However, according to the above configuration, since the storage element B is precharged before being connected to the non-aqueous secondary battery A, the storage element is used in a region corresponding to the charge / discharge depth used in the non-aqueous secondary battery A. B is prevented from being completely discharged.

In the method for manufacturing an assembled battery according to the present invention, the amount of charge for precharging is a capacity difference between the battery capacity C _B per unit cell of the storage element _B and the battery capacity C _A per unit cell of the non-aqueous secondary battery A. The following amount of electricity is preferable.

  According to the above configuration, even when the capacity of the electricity storage element B is larger than the capacity of the non-aqueous secondary battery A, the region used for charging / discharging in the electricity storage element B is shifted to an intermediate region by the preliminary charging, The power storage element B can be charged / discharged at a uniform charge / discharge depth.

Furthermore, in the method for manufacturing an assembled battery according to the present invention, the amount of charge for the preliminary charging includes a battery capacity C _B per unit cell of the power storage element B and a battery capacity C per unit cell of the non-aqueous secondary battery A. It is preferably about half of the capacity difference from _A.

  According to the above configuration, since the intermediate position of the charge / discharge depth of the non-aqueous secondary battery A substantially coincides with the intermediate position of the charge / discharge depth that can be used for charging / discharging the power storage element B, the deterioration of the power storage element B is further prevented. The

Further, the present invention mainly includes a plurality of non-aqueous secondary batteries A, and the plurality of non-aqueous secondary batteries A and at least one non-aqueous electrolyte for detecting internal resistance are connected in series. It is the difference between the internal resistance per cell of 75% internal resistance (R _A1) and the depth of discharge per cell at 25% depth of discharge in the non-aqueous secondary battery a (R _A2) △ R _A , the internal resistance (R _D1 ) per unit cell at a discharge depth corresponding to 25% of the discharge depth of the nonaqueous secondary battery A in the electricity storage element D, and the discharge depth 75 of the nonaqueous secondary battery A. % difference between the internal resistance (R _D2) per single cell in the corresponding discharge depth into a △ when the R _D, △ R _D of the electric device D is from △ R _a of the non-aqueous secondary battery a large and the battery capacity C _D per unit cell of the electric device D is _A method of manufacturing an assembled battery having a battery capacity CA larger than a battery capacity CA per unit cell of the non-aqueous secondary battery A, and before connecting the non-aqueous secondary battery A and the storage element D, the storage element D Is precharged.

  In the case of an assembled battery in which the capacity of the electricity storage element D is larger than the capacity of the non-aqueous secondary battery A so that the capacity of the non-aqueous secondary battery A constituting the main body of the assembled battery can be used effectively, for example, the uncharged of both batteries When the initial setting is made so that the discharge depth of the state matches, the discharge depth of the electricity storage element D becomes shallower than the discharge depth of the nonaqueous secondary battery at the end of charging of the assembled battery. Therefore, since there is a bias in the charge / discharge depth at the time of charge / discharge in the storage element D, the storage element D may be discharged until complete discharge, and the battery is likely to be deteriorated by the charge / discharge cycle. Deviation tends to occur in relation to internal resistance. However, according to the above configuration, since the storage element D is precharged before being connected to the non-aqueous secondary battery A, the storage element is used in a region corresponding to the charge / discharge depth used in the non-aqueous secondary battery A. D is prevented from being completely discharged.

In the assembled method for producing a battery of the present invention, the charge amount of the pre-charging, the capacity difference between the battery capacity C _A per unit cell of the battery capacity C _D and a non-aqueous secondary battery A per unit cell of the storage element D The following amount of electricity is preferable.

  According to the above configuration, even when the capacity of the electricity storage element D is larger than the capacity of the non-aqueous secondary battery A, the region used for charging / discharging in the electricity storage element D is shifted to an intermediate region by preliminary charging, The power storage element D can be charged / discharged at a uniform charge / discharge depth.

Furthermore, in the assembled method for producing a battery of the present invention, the charge amount of the preliminary charging, the battery capacity per unit cell in the battery capacity C _D and the non-aqueous secondary battery A per unit cell of the electric device D C It is preferably about half of the capacity difference from _A.

  According to the above configuration, since the intermediate position of the charge / discharge depth of the non-aqueous secondary battery A substantially coincides with the intermediate position of the charge / discharge depth that can be used for charging / discharging of the electricity storage element D, the deterioration of the electricity storage element D is further prevented. The

  According to the present invention, in an assembled battery mainly composed of a plurality of non-aqueous secondary batteries, a stable high output is obtained, and without complicating the apparatus of the power supply system, an inexpensive method is provided. The set end-of-charge period is accurately detected. In addition, by effectively preventing overcharge and overdischarge, a highly reliable assembled battery with high energy density can be obtained.

  FIG. 1 is a diagram schematically showing an example of an assembled battery composed of a non-aqueous secondary battery A and a storage element B of the present invention. The assembled battery (11) shown in FIG. 1 is an assembled battery in which a plurality of nonaqueous secondary batteries A (12) and one storage element B or storage element D (13) are connected in series. In the present invention, a plurality of non-aqueous secondary batteries A (12) are mainly used, and at least one power storage element B or power storage element D (13) is connected in series to the non-aqueous secondary battery A. If it is an assembled battery, the arrangement | sequence etc. of each cell are not specifically limited. For example, the location where the electricity storage element B or the electricity storage element D is connected to the nonaqueous secondary battery A may be the end portion or the inside of the assembled battery. Moreover, the form with which the assembled battery in which the some non-aqueous secondary battery A, the electrical storage element B, or the electrical storage element D was connected in series was connected in parallel may be sufficient. Further, a battery group in which a plurality of non-aqueous secondary batteries A are connected in parallel may be connected in series, and the battery group and power storage element B or power storage element D may be connected in series. Further, in a large power supply system in which a large number of nonaqueous secondary batteries A are used, two or more power storage elements B or power storage elements D may be connected in order to improve detection accuracy.

  Since the assembled battery of the present invention is also used for a large power supply system, the main body of the assembled battery is composed of a non-aqueous secondary battery A for the purpose of obtaining high output. For this reason, the output and energy density of the whole assembled battery are determined by the output and energy density of the non-aqueous secondary battery A. And in this invention, since the charging / discharging depth of the whole assembled battery is detected by the electrical storage element B or the electrical storage element D, the voltage change or internal resistance of the nonaqueous secondary battery A itself is within the range of the used charging / discharging depth. There is no need to make big changes. Therefore, as the non-aqueous secondary battery A constituting the main body of the assembled battery, a battery with little voltage change or internal resistance change can be used, and a stable high output is supplied to the device in a wide charge / discharge depth range.

On the other hand, in the battery pack composed only of the non-aqueous secondary battery A with little voltage change or internal resistance change, it is difficult to detect the charge / discharge depth due to the voltage change or internal resistance change. Therefore, in the present invention, the non-aqueous secondary battery A together with the non-aqueous secondary battery A is used as a voltage detection battery so that a high output can be obtained while accurately detecting the charge / discharge depth of the assembled battery. A non-aqueous electrolyte having a specific relationship with the non-aqueous secondary battery A as well as the non-aqueous secondary battery A as a storage element B having a non-aqueous electrolyte having a specific relationship with the non-aqueous secondary battery A Each of the storage elements D that are included is used. That is, the electricity storage device B of the present invention has a non-aqueous electrolyte, and the non-aqueous secondary battery A has a voltage per unit cell (V _A1 ) at a discharge depth of 25% and a unit cell at a discharge depth of 75%. the voltage difference between the voltage (V _A2) and △ V _a, the voltage per unit cell in the discharge depth corresponding to the depth of discharge of 25% of the non-aqueous secondary cell a in power storage device B and (V _B1) a non-aqueous when the voltage difference between the voltage (V _B2) per single cell in the discharge depth corresponding to the depth of discharge of 75% of the secondary battery a and △ V _B, the electricity storage device B △ V _B is a non-aqueous secondary battery Those having characteristics larger than ΔV A of _A are used. And as the electrical storage element D, it has a non-aqueous electrolyte, and the non-aqueous secondary battery A has an internal resistance (R _A1 ) per unit cell at a discharge depth of 25% and an internal unit per unit cell at a discharge depth of 75%. The difference from the resistance (R _A2 ) is ΔR _A, and the internal resistance (R _D1 ) per unit cell at the discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A in the storage element D when the difference between the internal resistance per cell in the discharge depth corresponding to the depth of discharge of 75% of the next cell a (R _D2) △ was R _D, △ R _D of the storage element D is the nonaqueous secondary battery Those having characteristics larger than ΔR A of _A are used.

By increasing the △ V _B of the storage element B than △ V _A nonaqueous secondary battery A, even when it is difficult detection of the charge-discharge depth of the small non-aqueous secondary battery A of voltage change, the voltage of the storage element B Is continuously decreased or increased in the normal use region of the charge / discharge depth of the non-aqueous secondary battery A, so that the set charge / discharge depth is accurately detected. Accordingly, by detecting the voltage of the storage element B instead of the voltage of the non-aqueous secondary battery A, the charge / discharge depth of the entire assembled battery is accurately detected, and overcharging and overdischarging of the entire assembled battery are effective. To be prevented. Further, a △ R _D of the storage element D by greater than △ R _A nonaqueous secondary battery A, even if difficult to detect the charging and discharging depth smaller non-aqueous secondary battery A internal resistance change, the electric storage element Since the internal resistance of D continuously decreases or increases in the normal use region of the charge / discharge depth of the non-aqueous secondary battery A, the set charge / discharge depth is accurately detected. Therefore, by detecting the internal resistance of the storage element D instead of the internal resistance of the non-aqueous secondary battery A, the charge / discharge depth of the entire assembled battery is accurately detected, and overcharging and overdischarging of the entire assembled battery are prevented. Effectively prevented. Furthermore, since the storage element B or the storage element D of the present invention is a battery having a non-aqueous electrolyte similar to the non-aqueous secondary battery A, the battery element B or the storage element D is more or less overcharged than the aqueous secondary battery. Even when a current flows, the influence of gas generation is suppressed, and a shift in charge / discharge depth of the electricity storage element B or the electricity storage element D is reduced.

  In the present invention, the discharge depth of the storage element B or the storage element D is set to the discharge depth corresponding to the discharge depth of the nonaqueous secondary battery A for the following reason.

  First, even when a non-aqueous secondary battery of the same type as the non-aqueous secondary battery A is used as the storage element B or the storage element D, the relationship between the discharge depth and voltage or the discharge depth and internal resistance varies between cells. May occur.

  Further, when the capacity of the storage element B or the storage element D is larger than the capacity of the non-aqueous secondary battery A, the ratio of the discharge depth of the non-aqueous secondary battery A is not necessarily the ratio of the discharge depth of the storage element B or storage element D. It does not match. For example, FIG. 2A is a characteristic diagram showing an example of the relationship between the discharge depth and the voltage in each unit cell of the nonaqueous secondary battery A and the storage element B of the present invention. Both batteries are lithium ion secondary batteries, but different types of positive electrode active materials are used so that the discharge depth and voltage characteristics are different. The non-aqueous secondary battery A in the upper diagram uses a lithium ion secondary battery with a capacity of 1000 mAh, and the storage element B in the lower diagram uses a lithium ion secondary battery with a capacity of 1200 mAh. FIG. 4 is a characteristic diagram showing an example of the relationship between the depth of discharge and the internal resistance in each unit cell of the non-aqueous secondary battery A and the storage element D of the present invention. Both batteries are lithium ion secondary batteries. The non-aqueous secondary battery A in the upper figure uses a lithium ion secondary battery with a capacity of 2000 mAh, and the storage element D in the lower figure uses a lithium ion secondary battery with a capacity of 2400 mAh. Yes. In FIG. 2A or FIG. 4, in order to show that the capacity of the electricity storage element B or the electricity storage element D is large, the discharge depth on the horizontal axis of the characteristic diagram of the electricity storage element B or the electricity storage element D in the lower figure is It is shown larger than the discharge depth of the non-aqueous secondary battery A. As shown in these figures, when the capacity of power storage element B or power storage element D is larger than the capacity of non-aqueous secondary battery A, 25% and 75% of the discharge depth of power storage element B or power storage element D are respectively The discharge depths of the non-aqueous secondary battery A do not coincide with 25% and 75%.

  Furthermore, in the present invention, when the capacity of the power storage element B or the power storage element D is larger than the capacity of the non-aqueous secondary battery A, the power storage element B or the power storage before connecting to the non-aqueous secondary battery A as described later. Since it is preferable to precharge the element D, in this case as well, the ratio of the depth of discharge of the electricity storage element B or the electricity storage element D does not coincide with the ratio of the depth of discharge of the nonaqueous secondary battery A. For example, FIG. 2B is a characteristic diagram in the case where the discharge depth of the storage element B is adjusted so that the intermediate position of the discharge depth of 50% of each unit cell of FIG. Even in such a case, the discharge depth of the non-aqueous secondary battery A does not coincide with the discharge depth of the storage element B. In FIG. 4, the power storage element D is precharged before being connected to the non-aqueous secondary battery A, and the discharge depth ratio of the power storage element D is the discharge depth of the non-aqueous secondary battery A. Will not match the percentage of. Incidentally, FIG. 5 is a characteristic diagram when the discharge depth of the electric storage element D is adjusted so that the intermediate position of the discharge depth of 50% of each unit cell in FIG. 4 matches.

  In view of the difference between the characteristics between the discharge depth of the storage element B and the voltage or the characteristics between the discharge depth and the internal resistance of the storage element D and the characteristics of the nonaqueous secondary battery A, Each discharge depth for detecting the voltage of the element B or detecting the internal resistance of the storage element D is set to a discharge depth corresponding to the discharge depth of the non-aqueous secondary battery A.

  Here, in the present invention, only the depth of discharge is to be compared, because the discharge depth of the secondary battery has a substantially opposite relationship to the charge depth, so the voltage difference or internal resistance difference at the discharge depth is the charge depth, respectively. This is because it substantially matches the voltage difference or internal resistance difference between the two, and the charge depth characteristic can be regarded as the discharge depth characteristic. Accordingly, in selecting the non-aqueous secondary battery A and the storage element B or the storage element D of the present invention, the relationship between the discharge depth and voltage or discharge depth and internal resistance of each battery is measured, and the discharge depth and voltage or discharge are measured. A non-aqueous secondary battery A and a storage element B, or a non-aqueous secondary battery A and a storage element D, each having a specific relationship between depth and internal resistance, are combined to form an assembled battery. The reason why the voltage or internal resistance at the discharge depths of 25% and 75% is to be compared is that the above range is frequently used as an assembled battery in electric vehicles, hybrid vehicles, etc., and high detection accuracy is required. It is.

The depth of discharge in the non-aqueous secondary battery A in the present invention is defined as 0% of the depth of discharge of each non-aqueous secondary battery A at the end-of-charge voltage at the initial full charge set during normal use of the assembled battery. The discharge depth of each nonaqueous secondary battery A at the end of discharge of the discharge end voltage set by the assembled battery is obtained as 100%. Therefore, a discharge depth of 25% is a state in which a single cell is charged at 0.2 C (5 hour rate) to the end-of-charge voltage based on the discharge depth, and then a capacity of 25% is discharged. 75% means a state in which the battery is charged at 0.2 C up to the end-of-charge voltage, and then the capacity of 75% is discharged. The open terminal voltage at each discharge depth is set to V _A1 and V _A2 , respectively. In the storage element B, the discharge depth and open terminal voltages V _B1 and V _B2 corresponding to 25% and 75% of the discharge depth of the non-aqueous secondary battery A are respectively determined from the discharge depth and voltage curve measured in the same manner. Desired. Similarly, R _A1 and R _A2 are internal resistances determined from voltages when a certain current is taken out at a discharge depth of 25% and 75% in the nonaqueous secondary battery A, respectively. And in the electrical storage element D, the discharge of the non-aqueous secondary battery A at the discharge depth corresponding to 25% and 75% of the discharge depth of the non-aqueous secondary battery A from the discharge depth and the internal resistance curve measured in the same manner. The depth of discharge corresponding to 25% and 75% of the depth and the internal resistances R _D1 and R _D2 are obtained, respectively.

In the present invention, △ V _B of the storage element B is larger than △ V _A nonaqueous secondary battery A, preferred because a large voltage change can be expected stability and power storage device B outputs of the non-aqueous secondary cell A . △ more preferably the ratio of V _{B /} △ V _A is 2 or more, more preferably 5 or more, most preferably 10 or more. On the other hand, the upper limit of the ratio is not particularly limited, but is preferably 20 or less in consideration of the influence on the output change of the entire assembled battery.

Also, △ R _D of the storage element D is larger than △ R _A nonaqueous secondary battery A, preferred because it can expect large internal resistance change of the stability and the storage device D of the output of the non-aqueous secondary battery A is. The ratio of ΔR _D / ΔR _A is more preferably 2 or more, and more preferably 8 or more. On the other hand, the upper limit of the ratio is not particularly limited, but is preferably 20 or less in consideration of the influence on the output change of the entire assembled battery.

In the present invention, the capacitance C _D of the capacitance C _B or electric device D of the storage element B are who are larger than the capacity C _A non-aqueous secondary battery A is preferred. When the storage element B or the storage element D having a capacity larger than that of the non-aqueous secondary battery A is used, the use area of the charge / discharge depth of the non-aqueous secondary battery A is overcharged or overcharged of the storage element B or the storage element D. Since it is away from the discharge region, the deterioration of the storage element B or the storage element D is reduced, and the deviation from the setting time of the relationship between the charge / discharge depth and the voltage or the relationship between the charge / discharge depth and the internal resistance is reduced. Is done. In the assembled battery of the present invention, charging / discharging is regulated by detecting the voltage of the storage element B or the internal resistance of the storage element D, but the storage element B or the capacity larger than the capacity of the non-aqueous secondary battery A If the storage element D is used, the charge / discharge is not completed in a state where the non-aqueous secondary battery A has the charge / discharge capacity, so the capacity of the non-aqueous secondary battery mainly composed of the assembled battery is increased. A fully assembled battery with a high energy density can be obtained.

The capacity C _B of the electricity storage element B is a ratio C _B / C _A to the capacity C _A of the non-aqueous secondary battery A, and is preferably 1.05 or more, and more preferably 1.1 or more. Further, the capacity C _D of the electricity storage element D is 1.05 or more, more preferably 1.1 or more, as a ratio C _D / C _A to the capacity C _A of the non-aqueous secondary battery A. On the other hand, if the ratio is too large, the volume occupied by the storage element B or the storage element D in the assembled battery becomes too large, and the energy density of the assembled battery decreases, so 1.5 or less is preferable and 1.2 or less is preferable. More preferred. In the present invention, the capacity of each unit cell is a capacity obtained by the above-described measurement conditions for the depth of discharge.

  Next, a specific configuration of the non-aqueous secondary battery A and the storage element B or the storage element D of the present invention will be described.

  As the non-aqueous secondary battery A constituting the main body of the assembled battery of the present invention, a lithium ion secondary battery, a lithium polymer secondary battery, or the like that is lightweight and can provide high output is used.

The non-aqueous secondary battery A is a battery using a transition metal oxide as a positive electrode active material, and is preferable because a battery having a high discharge voltage can be obtained. As the positive electrode active material, specifically, for example, cobalt-based oxides such as LiCoO _2, a nickel-based oxides such as LiNiO _2, other manganese oxide such as _{LiMn 2 O 4, LiNi x Al} y Co An oxide in which a plurality of transition metals such as _z O ₂ is dissolved is given.

  In particular, when the positive electrode of the nonaqueous secondary battery A contains at least one selected from an iron phosphate compound and a nickel manganese spinel oxide as a positive electrode active material, these positive electrode active materials have voltage fluctuations with respect to the charge / discharge depth. Or, since the internal resistance variation is very small, it is preferable as the positive electrode material of the non-aqueous secondary battery A.

As the iron phosphate compound, the general formula Li _z1 Fe _1-y1 M ¹ _y1 PO ₄ (where 0 <z ¹ ≦ 1 and 0 ≦ y ¹ <1 and M ¹ is Nb, Mg, Ti, Zr , Ta, W, Mn, and Ni). As the nickel-manganese spinel oxide represented by the general formula ^{_{Li z2 Mn 1.5-y2 M 2}} y2 Ni 0.5 + α O 4 ( provided that at 0 ^{<z 2} ≦ 1, at 0 ≦ ^y 2 <0.3, -0.1 ≦ α ≦ 0.1, and M ² is any one selected from Co and Ti).

  The positive electrode of the non-aqueous secondary battery A is produced, for example, by applying a positive electrode active material, a binder, and a mixture containing other additives as necessary to the positive electrode current collector and rolling.

Specific examples of the negative electrode active material of the non-aqueous secondary battery A include, for example, carbon materials such as graphite and amorphous carbon, metals such as lithium and tin, or alloys and oxides thereof, LiTi _x O Metal oxides such as _y and LiMn ₂ O ₄ are preferred.

Since the voltage characteristics or internal resistance characteristics of the non-aqueous secondary battery are mainly influenced by the types of the positive electrode active material and the negative electrode active material, the positive electrode active material of the non-aqueous secondary battery A is low among the above active materials. It is preferable to use an active material capable of obtaining a voltage difference or a low internal resistance difference. In the present invention, in view of obtaining a stable high output by the battery pack, the voltage difference △ V _A, preferably 150mV or less, more preferably 100mV or less. Among these active materials, positive electrode using LiNi _0.5 Mn _1.5 O ₄ or iron phosphate compound which is 5V class spinel type lithium manganese oxide as positive electrode active material, and graphite as negative electrode active material. non-aqueous secondary battery and the negative electrode are combined, the charge and discharge potential of the intermediate portion is particularly flat, there is a case where △ V _a is 100mV or less. The non-aqueous secondary battery in which the positive electrode active material and the negative electrode active material are combined has a particularly flat internal resistance change with respect to the charge / discharge depth. Therefore, while stable high output can be obtained, voltage detection or internal resistance detection becomes difficult, and the nonaqueous secondary battery in which these active materials are combined exhibits particularly excellent effects in the present invention.

  The negative electrode of the non-aqueous secondary battery A is produced, for example, by applying a negative electrode active material, a binder, and a mixture containing other additives as necessary to the negative electrode current collector and rolling. When a metal such as lithium or an alloy is used for the negative electrode, the rolled plate may be used as the negative electrode.

The nonaqueous electrolyte of the nonaqueous secondary battery A of the present invention is not only a liquid electrolyte used for a lithium ion secondary battery, but also a gel or solid electrolyte used for a lithium polymer secondary battery. Good. Examples of the liquid electrolyte include nonaqueous electrolytes containing a lithium salt such as LiPF _{6 in} an organic solvent such as ethylene carbonate and propylene carbonate. Examples of the gel or solid electrolyte include polyethylene oxide containing a lithium salt.

As the electricity storage element B or the electricity storage element D of the present invention, an electric double layer capacitor having a nonaqueous electrolyte, a nonaqueous secondary battery, or the like is used. Potential difference △ V _B of the storage element B is not particularly limited as larger than the potential difference △ V _A nonaqueous secondary battery A, considering the detection accuracy of the common sensing element, is preferably at least 200 mV, more than 300mV More preferably, 500 mV or more is most preferable. On the other hand, considering the influence on the voltage change of the entire assembled battery, 1300 mV or less is preferable, and 1000 mV or less is more preferable. The internal resistance difference △ R _D of the storage element D is not particularly limited as greater than the internal resistance difference △ R _A nonaqueous secondary battery A.

  When an electric double layer capacitor is used as the storage element B, a large voltage change (1000 mV or more) can be obtained according to the depth of discharge, so that accurate detection of the voltage of the storage element B is easy. This is preferable because the end voltage can be accurately detected.

  FIG. 2C is a characteristic diagram showing an example of the relationship between the discharge depth and the voltage of each unit cell of the non-aqueous secondary battery A and the storage element B of the present invention, and the upper diagram shows the capacity as the non-aqueous secondary battery A. When a 1000 mAh lithium ion secondary battery is used, the following figure shows a case where an electric double layer capacitor having a capacity of 1000 mAh is used as the storage element B. As shown in FIG. 2 (c), since the voltage of the electric double layer capacitor changes linearly by charging / discharging from the non-aqueous secondary battery A, the assembled battery for a power supply system requiring strict charge / discharge control. Is preferably used.

  In the present invention, when an electric double layer capacitor is used as the electricity storage element B, an electric double layer capacitor having a non-aqueous electrolyte mainly composed of an organic solvent such as propylene carbonate is used in order to reduce the influence of gas generation. The electric double layer capacitor may contain water as an electrolyte component for reducing the specific resistance, but an organic solvent is used as a main component because gas generation becomes significant in an electrolyte solution mainly composed of a water component. .

Examples of the non-aqueous electrolyte of the electric double layer capacitor include a non-aqueous electrolyte in which an electrolyte salt such as triethylmethylammonium fluoroborate (TEMA · BF ₄ ) is dissolved in the above organic solvent.

  In the present invention, as the electric double layer capacitor, those produced by a conventionally known production method can be used. In accordance with the characteristics of the assembled battery, an electric double layer capacitor capable of obtaining a predetermined voltage, capacity, etc. required when used as a part of the power generation element is appropriately selected.

  In the present invention, when a non-aqueous secondary battery is used as the power storage element B, the energy density of the non-aqueous secondary battery is large, so that a reduction in the energy density of the entire assembled battery is prevented and charging / discharging of the power storage element B is performed. This is preferable because the relationship between depth and voltage is less likely to deviate from the initial setting. Further, when a non-aqueous secondary battery is used as the storage element D, similarly, the non-aqueous secondary battery has a large energy density, so that a decrease in the energy density of the entire assembled battery is prevented and the charging of the storage element D is also prevented. This is preferable because the relationship between the depth of discharge and the internal resistance is less likely to deviate from the initial setting.

When a non-aqueous secondary battery is used as the electricity storage element B or the electricity storage element D, a non-aqueous secondary battery having the same positive electrode, negative electrode, and non-aqueous electrolyte structure as the non-aqueous secondary battery A described above is used. Among these, for △ V _B of the storage element B is required to be greater than the △ V _A nonaqueous secondary battery A, it is preferable to use an active material showing a large voltage change in accordance with the depth of discharge. Further, since △ R _D of the storage element D is required to be greater than the △ R _A nonaqueous secondary battery A, it is preferable to use an active material showing large internal resistance changes according to the depth of discharge.

Such a positive electrode active material may contain a lithium oxide represented by LiMO ₂ (wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, and Mg). preferable. In particular, a metal oxide in which a plurality of transition metals such as LiNi _x Al _y Co _z O ₂ is dissolved is preferable.

  The negative electrode active material preferably contains at least one material selected from amorphous carbon, metals such as tin or alloys thereof, and metal oxides. In addition, when aiming at low cost by sharing the material of the non-aqueous secondary battery A and the material of the electricity storage element B or the electricity storage element D, for example, it is preferable to use the same graphite for the negative electrode.

  In the present invention, the positive electrode of the non-aqueous secondary battery A is preferably a positive electrode whose average discharge potential based on the Li potential of the positive electrode is lower than the average discharge potential based on the Li potential of the positive electrode of the storage element B or the storage element D.

  If the battery pack is composed of a combination of the non-aqueous secondary battery A having the relationship of the average discharge potential of the positive electrode as described above and the electricity storage element B or the electricity storage element D, the electricity storage element B or the electricity storage element D is non-aqueous when used. The potential of the secondary battery A does not become higher, the deterioration of the storage element B or the storage element D becomes slower than the deterioration of the non-aqueous secondary battery A, and the capacity of the assembled battery becomes the capacity of the deteriorated storage element B or storage element D It is prevented from being regulated by.

Further, in the present invention, when a non-aqueous secondary battery is used as the storage element B or the storage element D, the amount of Mn contained in the positive electrode of the non-aqueous secondary battery A is determined in the positive electrode of the storage element B or the storage element D. It is preferable that the amount of Mn contained in is smaller. For example, when a manganese-based oxide is used as the positive electrode active material, manganese ions eluted from the positive electrode due to charge / discharge move to the negative electrode, and a film is formed on the negative electrode, thereby reducing characteristics such as capacity. Therefore, if the battery pack is a combination of the nonaqueous secondary battery A having the relationship of Mn amount as described above and the storage element B or the storage element D, the Mn amount in the positive electrode of the storage element B or the storage element D Is smaller than the amount of Mn in the positive electrode of the non-aqueous secondary battery A, the deterioration of the storage element B or the storage element D is slower than the deterioration of the non-aqueous secondary battery A. For this reason, the capacity of the assembled battery is prevented from being regulated by the capacity of the storage element B or the storage element D that has deteriorated even though the non-aqueous secondary battery A is in a usable state. As such a combination, when LiMn _1.5 Ni _0.5 O ₄ is used for the positive electrode active material of the non-aqueous secondary battery A, the positive electrode active material of the electricity storage device B or the electricity storage device D includes LiCoO ₂ or Examples include a positive electrode active material not containing manganese such as LiNiO ₂ and a positive electrode active material having a low manganese content such as LiNi _0.4 Mn _0.3 Co _0.3 O ₂ .

  The assembled battery of the present invention is manufactured by connecting a plurality of nonaqueous secondary batteries A having the above characteristics and at least one power storage element B or power storage element D in series. And this power supply system is manufactured by integrating this assembled battery with a voltage detection device or an internal resistance detection device, an overcharge prevention circuit, an overdischarge prevention circuit, etc.

  In the present invention, in the case of manufacturing an assembled battery in which a nonaqueous secondary battery A and a storage element B or a storage element D having a capacity larger than the capacity of the nonaqueous secondary battery A are used in combination, Before connecting secondary battery A and power storage element B or power storage element D, it is preferable to precharge power storage element B or power storage element D.

  As shown in FIG. 2A, when the nonaqueous secondary battery A and the storage element B have different capacities, the discharge depth of the storage element B deviates from the discharge depth of the nonaqueous secondary battery A. . For this reason, if the power storage element B having a large capacity is charged with a predetermined amount of electricity in advance, it is connected to the non-aqueous secondary battery A in a state where the depth of discharge is shifted by the amount of electricity for the preliminary charge. FIG. 2B is a combination of the non-aqueous secondary battery A and the storage element B in FIG. 2A, and the amount of electricity (100 mAh) is about half the capacity difference between the storage element B and the non-aqueous secondary battery A. FIG. 6 is a characteristic diagram when the storage element B is precharged.

  As shown in FIG. 2 (b), the discharge depth region used for charging / discharging the electricity storage element B is shifted to the middle part of the discharge depth region where the electricity storage element B can be charged / discharged. Due to the adjustment by the preliminary charging, the voltage range used in the power storage element B having a large voltage difference is also an intermediate portion, so that the bias of the voltage at the time of charging and discharging is reduced. Since it leaves | separates from the area | region of an overcharge or overdischarge, degradation of the electrical storage element B is prevented.

  Further, as shown in FIG. 4, when the capacities of both the non-aqueous secondary battery A and the storage element D are different, the discharge depth of the storage element D is different from the discharge depth of the non-aqueous secondary battery A. For this reason, if the storage element D having a large capacity is charged in advance with a predetermined amount of electricity, it is connected to the non-aqueous secondary battery A in a state where the depth of discharge is shifted by the amount of electricity for preliminary charging. FIG. 4 is a characteristic diagram when the electricity storage element D is precharged with about half the amount of electricity (200 mAh) of the capacity difference between the electricity storage element D and the non-aqueous secondary battery A.

  As shown in FIG. 4, the discharge depth region used for charging / discharging the electricity storage element D is shifted to an intermediate portion of the discharge depth region where the electricity storage element B can be charged / discharged. Due to the adjustment by the preliminary charging, the charging / discharging range used in the power storage element D having a large internal resistance difference becomes an intermediate portion, so that the power storage element D moves away from the overcharge or overdischarge region. Deterioration is prevented.

  In the present invention, the amount of electricity for the preliminary charging may be less than or equal to the capacity difference between the storage element B and the non-aqueous secondary battery A, or less than or equal to the capacity difference between the storage element D and the non-aqueous secondary battery A. It is 20-50% of the capacity | capacitance difference of both batteries, More preferably, it is about half. If the amount of electricity for pre-charging is about half the capacity difference between the two batteries, the middle position of the discharge depth of both batteries will be approximately the same, so both batteries will be charged in the middle of the usable area. It is discharged and deterioration is reduced.

  Next, a power supply system in which the assembled battery of the present invention is used will be described. FIG. 3 is a circuit diagram showing an example of the power supply system of the present invention. The power supply system (21) includes a main power supply unit (22) composed of a plurality of nonaqueous secondary batteries A (12) and a plurality of nonaqueous systems. The assembled battery (11) including the monitoring unit (23) including the power storage element B or the power storage element D (13) connected in series with the secondary battery A (12), and the voltage or power storage of the power storage element B (13) It is comprised from the control part (24) which detects the internal resistance of the element D (13), and controls charging / discharging of the whole assembled battery based on the detected voltage or internal resistance.

  As a control part (24) used for the power supply system of this invention, the apparatus currently used for the charging / discharging control of the conventional assembled battery is used. Specifically, for example, the control unit (24) includes a detection unit for detecting the voltage across the storage element B (13) or a detection unit for detecting the internal resistance of the storage element D (13). The storage means to which the data table of the charge / discharge depth and voltage of the storage element B prepared in advance was input, or the storage means to which the data table of the charge / discharge depth and internal resistance of the storage element D was input, was detected. Charge / discharge depth detection means for determining the charge / discharge depth of the storage element B (13) based on the voltage, or charge / discharge depth detection means for determining the charge / discharge depth of the storage element D (13) based on the detected internal resistance. I have. And charging / discharging of the whole assembled battery (11) is managed based on the charging / discharging depth of the obtained electrical storage element B or electrical storage element D (13).

  In the power supply system as described above, the nonaqueous secondary battery A is based on the relationship between the charge / discharge depth of the nonaqueous secondary battery A and the voltage obtained in advance based on the charge / discharge conditions set in the power supply system. The charge / discharge depth of power storage element B corresponding to the charge / discharge depth is determined, and the relationship between the detected voltage and the charge / discharge depth of the assembled battery is set. The range of the charge / discharge depth used in the non-aqueous secondary battery A during charging / discharging of the assembled battery is set in consideration of the characteristics required for the power supply system in which the assembled battery is incorporated. For example, only a narrow range of charge / discharge depth with little voltage change may be used in a system that requires extremely stable high output, and a wide range of charge / discharge is required in a system that requires large capacity and long-term use. Depth may be used. Even in an assembled battery used in such a power supply system with different charge / discharge depths, a voltage difference between discharge depths in a range (25 to 75%) frequently used as a non-aqueous secondary battery in the present invention. Since the storage element B is selected based on the above, it can be applied without being limited by the charge / discharge depth of the system.

  Alternatively, in the power supply system as described above, based on the relationship between the charge / discharge depth of the nonaqueous secondary battery A and the internal resistance obtained based on the charge / discharge conditions set in advance in the power supply system, the nonaqueous two The charge / discharge depth of the storage element D corresponding to the charge / discharge depth of the secondary battery A is determined, and the relationship between the detected internal resistance and the charge / discharge depth of the assembled battery is set. The range of the charge / discharge depth used in the non-aqueous secondary battery A during charging / discharging of the assembled battery is set in consideration of the characteristics required for the power supply system in which the assembled battery is incorporated. For example, in a system that requires extremely stable high output, only a narrow range of charge / discharge depth with little internal resistance change may be used, and in a system that requires large capacity and long-term use, a wide range of charge / discharge is available. The depth of discharge may be used. Even in an assembled battery used for such power supply systems with different charge / discharge depths, the internal resistance between discharge depths in the range (25 to 75%) frequently used as a non-aqueous secondary battery in the present invention. Since the electrical storage element D is selected on the basis of the difference, it can be applied without being limited by the charge / discharge depth of the system.

  Specific embodiments of the assembled battery of the present invention will be described below, but the present invention is not limited to these embodiments.

<Embodiment 1>
In the present embodiment, an assembled battery composed of a combination of a lithium ion secondary battery as the non-aqueous secondary battery A and the same type of lithium ion secondary battery as the power storage element B has been studied.

[Production of single cell]
(Lithium ion secondary battery-1: L-1)
100 parts by mass of LiNi _0.5 Mn _1.5 O ₄ as a positive electrode active material, 2.5 parts by mass of acetylene black as a conductive agent, and ₄ parts by mass of polyvinylidene fluoride (PVDF) as a binder are kneaded with a dispersion medium. A slurry was made. This slurry was applied to both sides of a 15 μm thick aluminum foil as a current collector, dried and rolled, and then cut into a predetermined size to produce a positive electrode plate.

  Separately from the above, 100 parts by mass of graphite as a negative electrode active material and 6 parts by mass of PVDF as a binder were kneaded with a dispersion medium to prepare a negative electrode slurry. This slurry was applied to both sides of a 10 μm thick copper foil as a current collector, dried and rolled, and then cut into a predetermined size to produce a negative electrode plate.

Using the positive electrode plate and the negative electrode plate produced as described above, the electrode body was produced by spirally winding the two electrodes so as to face each other with a 27 μm polyethylene separator interposed therebetween. This electrode body is inserted into a battery can, and an electrolytic solution in which 1.5M LiBF ₄ is dissolved in a solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a volume ratio of 1: 3 is injected. Thus, a lithium ion secondary battery-1 (L-1) of 18650 size having a battery can outer diameter of 18 mm and a height of 65 mm was produced.

  The battery produced as described above had a capacity of 1000 mAh when the end-of-charge voltage was 4.85 V and the end-of-discharge voltage was 3.0 V at a current value of 0.2 C.

(Lithium ion secondary battery-2: L-2)
LiNi _0.8 Al _0.1 Co _0.2 O ₂ is used as the positive electrode active material instead of LiNi _0.5 Mn _1.5 O _{4 so} that the capacity becomes 1.2 times the capacity of L-1. A lithium ion secondary battery-2 (L-2) was produced in the same manner as L-1, except that the coating amount was changed to 1 and the coating amount of the negative electrode was changed accordingly.

  The battery produced as described above had a capacity of 1200 mAh when the end-of-charge voltage was 4.2 V and the end-of-discharge voltage was 3.0 V at a current value of 0.2C.

(Lithium ion secondary battery-3: L-3)
A lithium ion secondary battery-3 (L-3) was produced in the same manner as L-2 except that amorphous carbon was used instead of graphite as the negative electrode active material.

  The battery produced as described above had a capacity of 1200 mAh when the end-of-charge voltage was 4.2 V and the end-of-discharge voltage was 3.0 V at a current value of 0.2C.

(Lithium ion secondary battery-4: L-4)
A lithium ion secondary battery-4 (L-4) was produced in the same manner as L-2, except that the battery volume was increased and the capacity was changed to 2000 mAh.

[Production of assembled battery]
(Battery-1)
L-1 and L-2 produced as described above are used, and after each battery is activated by charging / discharging and aging, preliminary charging is performed for L-2 used as power storage element B before connection. Was done. In the preliminary charging, an amount of electricity that is half of the capacity difference between the capacity L-2 used as the electricity storage element B and the capacity L-1 used as the non-aqueous secondary battery A was charged. Next, ten L-1s were connected in series, and one L-2 was connected in series as a storage element B to the end thereof, thereby producing assembled battery-1.

(Battery-2)
An assembled battery-2 was produced in the same manner as the assembled battery-1, except that L-3 was used as the power storage element B in the production of the assembled battery-1.

(Battery-3)
In the production of the assembled battery-1, the assembled battery-3 is the same as the assembled battery-1, except that the amount of electricity for the precharge is 20% of the capacity difference between L-2 and L-1. Made.

(Battery-4)
An assembled battery-4 was produced in the same manner as the assembled battery-1, except that L-4 was used as the electricity storage element B in the production of the assembled battery-1.

(Battery-5)
In the production of the assembled battery-1, an assembled battery 5 was produced in the same manner as the assembled battery-1, except that the preliminary charging was not performed.

(Battery-6)
In the production of the assembled battery-1, 11 L-1s were connected in series to produce an assembled battery-6. In addition, since the same L-1 connected to the terminal was used as the electricity storage element B, the preliminary charging was not performed.

The voltage V _A1 , V _A2 , the voltage difference ΔV _A and the capacity C _A , L-2 at the discharge depths of 25% and 75% in the L-1 cell in each assembled battery produced as described above. Table 1 shows voltages V _B1 , V _B2 , voltage difference ΔV _B, and capacity C _B at discharge depths corresponding to the above-described discharge depths of L-4.

  About each assembled battery, the shift | offset | difference of the output of the whole assembled battery and the charge / discharge depth after a cycle was evaluated. As for the output of the assembled battery, the voltage and current after 10 seconds were measured when discharging was performed at a current of 2 A at a discharge depth of 50%, and the output of the assembled battery-6 was evaluated as 100%.

  The shift in the charge / discharge depth after the cycle is a cycle test in which charge / discharge control is performed with the voltage of the storage element B at the discharge depth corresponding to 25% and 75% of the discharge depth of the non-aqueous secondary battery A at 1C (number of cycles: 50 times) is performed in each assembled battery, and at the initial setting, the storage element B stops discharging at a voltage indicating a discharge depth of 50%, and L-1 of each assembled battery at that time is measured, and the discharge depth and The evaluation was based on the deviation of the discharge depth from the initially set discharge depth of 50%. Table 1 shows the results.

As shown in Table 1, the non-aqueous secondary battery A, a power storage device B having a voltage difference △ V 3 to 9 times than _A large voltage difference △ V _B of the non-aqueous secondary battery A is combined with By configuring the assembled battery, the assembled battery with a small deviation from the initial discharge depth of the assembled battery can be obtained for the nonaqueous secondary battery A even after the cycle. In addition, a lithium ion secondary battery with a large voltage change is used for the storage element B, but since one storage element B is used for 10 non-aqueous secondary batteries A, the output density The decline of the is also suppressed. Therefore, since the assembled battery of the present invention has high output and voltage detection is performed by the power storage element B having a large voltage change, even when the non-aqueous secondary battery A having a flat voltage change is mainly used, the charge / discharge end stage is performed. Can be detected accurately, and there is little shift in the charge / discharge depth, and overcharge and overdischarge are effectively prevented. In each of the assembled batteries -1 to -4, a storage element B having a capacity larger than that of the nonaqueous secondary battery A is used, but a predetermined amount of electricity is reserved for adjusting the discharge depth. Since the battery is charged, there is little voltage deviation during charging / discharging of the assembled battery, and complete discharge of the electricity storage element B is prevented, so that an assembled battery with reduced deterioration and less deviation in charge / discharge depth can be obtained.

Depending on the device to which the power supply system is applied, various active materials having different charge / discharge characteristics are used in order to improve various characteristics of the battery such as life characteristics and thermal stability. For example, when a transition metal oxide is used as the positive electrode active material, the metal site is replaced with a metal element such as Ni, Co, Mn, Fe, Cr, Al, Ti, Mg, Zn, or F at the oxygen site. May be replaced. Depending on the composition of the positive electrode active material and the capacity balance between the positive electrode and the negative electrode, the relationship of the voltage difference between the nonaqueous secondary battery A and the storage element B may change. However, even in such a case, when the voltage difference △ V _B potential difference △ V _A larger battery used as a power storage device B, the effect of the present invention is obtained.

<Embodiment 2>
In the present embodiment, an assembled battery composed of a combination of a lithium ion secondary battery as the nonaqueous secondary battery A and an electric double layer capacitor as the power storage element B has been studied.

[Production of single cell]
(Capacitor-1: C-1)
A device in which activated carbon was applied to an aluminum foil as a positive electrode and a negative electrode was wound in a spiral shape so that both electrodes face each other with a separator interposed therebetween. This element was inserted into a case, and a capacitor-1 (C-1) was fabricated by impregnating the element with a nonaqueous electrolyte in which an electrolyte salt was dissolved in a solvent.

  The capacitor produced as described above had a current value of 0.2 C, a charge end voltage of 2.5 V, and a capacity of 1000 mAh when the discharge end voltage was 0 V.

(Capacitor-2: C-2)
Capacitor-2 (C-2) was prepared in the same manner as C-1, except that a positive electrode and a negative electrode having a large electrode area were used so that the capacitance was 1.2 times in the production of C-1, and the element was enlarged. Was made.

  The battery produced as described above had a current value of 0.2 C, a charge end voltage of 2.5 V, and a capacity of 1200 mAh when the discharge end voltage was 0 V.

[Production of assembled battery]
(Battery-7)
In the same manner as in the assembled battery-1, the assembled battery -7 is obtained by using the C-1 produced as described above as the power storage element B and the L-1 produced in the first embodiment as the non-aqueous secondary battery A. Made. Since L-1 and C-1 have the same capacity, no preliminary charging was performed.

(Battery-8)
In the production of the assembled battery-1, an assembled battery -8 was produced in the same manner as the assembled battery-1, except that C-2 was used as the electricity storage element B.

  About the assembled battery-7 and the assembled battery-8 which were produced as mentioned above, evaluation of the shift | offset | difference of the output similar to Embodiment 1 and the charge / discharge depth after a cycle was performed. The evaluation results are shown in Table 2 together with the assembled battery-6.

  As shown in Table 2, the assembled battery-7 and the assembled battery-8, in which the electric double layer capacitor is used as the storage element B, are discharged more than the assembled battery-6 composed of only the same lithium ion secondary battery. It can be seen that the battery pack has a small depth error. Also, regarding the output of the assembled battery, the outputs of the assembled battery-7 and the assembled battery-8 are slightly lower than those of the assembled battery-6 consisting of only lithium ion secondary batteries, but the difference is also 6% or less. It turns out that the assembled battery which has a substantially equivalent energy density is obtained.

<Embodiment 3>
In the present embodiment, an assembled battery composed of a combination of a lithium ion secondary battery as the non-aqueous secondary battery A and a lithium ion secondary battery of the same type as the power storage element D has been studied.

[Production of single cell]
(Lithium ion secondary battery-5: L-5)
100 parts by mass of LiFePO ₄ as a positive electrode active material, 10 parts by mass of acetylene black as a conductive agent, and ₄ parts by mass of polyvinylidene fluoride (PVDF) as a binder were kneaded with a dispersion medium to prepare a positive electrode slurry. This slurry was applied to both sides of a 15 μm thick aluminum foil as a current collector, dried and rolled, and then cut into a predetermined size to produce a positive electrode plate. In addition, since the electronic resistance of LiFePO ₄ is low, an active material having a small particle size of about 100 nm was used.

  Separately from the above, 100 parts by mass of graphite as a negative electrode active material and 6 parts by mass of PVDF as a binder were kneaded with a dispersion medium to prepare a negative electrode slurry. This slurry was applied to both sides of a 10 μm thick copper foil as a current collector, dried and rolled, and then cut into a predetermined size to produce a negative electrode plate.

Using the positive electrode plate and the negative electrode plate manufactured as described above, the electrode body was manufactured by being spirally wound so that both electrodes face each other with a 20 μm polyethylene separator interposed therebetween. This electrode body was inserted into a battery can, and 1.4 M LiPF ₄ was added to a solvent in which ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed at a volume ratio of 1: 1: 8. The lithium ion secondary battery-5 (L-5) of 26650 size having a battery can outer diameter of 26 mm and a height of 65 mm was produced.

  The battery produced as described above had a capacity of 2000 mAh when the end-of-charge voltage was 3.7 V and the end-of-discharge voltage was 2.0 V at a current value of 0.2C.

(Lithium ion secondary battery-6: L-6)
LiNi _1/3 Mn _1/3 Co _1/3 O ₂ was used instead of LiFePO ₄ as the positive electrode active material, and the coating amount was changed so that the capacity was 1.2 times the capacity of L-5. Accordingly, a lithium ion secondary battery-6 (L-6) was produced in the same manner as L-5, except that the coating amount of the negative electrode was changed.

  The battery produced as described above had a capacity of 2400 mAh when the end-of-charge voltage was 4.2 V and the end-of-discharge voltage was 2.5 V at a current value of 0.2C.

FIG. 4 shows changes in internal resistance with respect to the depth of discharge for L-5 (upper diagram) and L-6 (lower diagram). Here, the internal resistance of FIG. 4 was measured as follows. After adjusting to each depth of discharge, the open circuit voltage _{V x} is measured, then dividing the voltage difference between the voltage _{V y} when performing a 10 sec discharge 2A a _(V x -V _y) at a current value (2A) Thus, the internal resistance was obtained.

  As shown in FIG. 4, the change in internal resistance is much smaller in L-5 than in L-6. Therefore, by using an assembled battery using L-5, it is possible to obtain an assembled battery having a small internal resistance difference, that is, a small output fluctuation, regardless of the charge / discharge depth. Constructing a power supply system with a battery pack with small output fluctuations has the advantage that the power supply system design can be facilitated without considering the power drop due to the charge / discharge depth.

[Production of assembled battery]
(Battery-9)
L-5 and L-6 produced as described above are used, and after each battery is activated by charge / discharge and aging, L-6 used as a storage element D before connection is precharged. Was done. In the preliminary charging, a half of the capacity difference between the capacity of L-6 used as the electricity storage element D and the capacity of L-5 used as the non-aqueous secondary battery A was charged. Next, ten L-5s were connected in series, and one L-6 was connected in series as a power storage element D to the end thereof, thereby producing an assembled battery-9.

(Battery-10)
In the production of the assembled battery-9, 11 L-5s were connected in series to produce the assembled battery-10. In addition, since the same L-5 connected to the terminal was used as the electricity storage element D, the preliminary charging was not performed.

Corresponds to the internal resistance difference ΔR _A at the discharge depth of 25% and 75% in the L-5 unit cell and the discharge depth of the capacity C _A , L-6 in each assembled battery produced as described above. internal resistance difference in the depth of discharge of △ R _D, and the capacitance C _D shown in Table 3.

  About each assembled battery, the shift | offset | difference of the output of the whole assembled battery and the charge / discharge depth after a cycle was evaluated. The output of the battery pack was calculated from the voltage and current after 10 seconds when the battery was discharged at a current of 10 A at a discharge depth of 50%, and the output of the battery pack-10 was evaluated as 100%.

  The shift in the charge / discharge depth after the cycle is a cycle test in which charge / discharge control is performed with the voltage of the storage element D at a discharge depth corresponding to 25% and 75% of the discharge depth of the nonaqueous secondary battery A at 1C (number of cycles: 50 times) is performed in each assembled battery, and at the initial setting, discharging is stopped at a voltage at which the storage element D has a discharge depth of 50%, and L-5 of each assembled battery at that time is measured. The evaluation was based on the deviation of the discharge depth from the initially set discharge depth of 50%. Table 3 shows the results.

As shown in Table 3, the non-aqueous secondary battery A, the electric device D having an internal resistance difference △ about 8 times more R _A high internal resistance difference △ R _D of the non-aqueous secondary cell A are combined By configuring the assembled battery, the non-aqueous secondary battery A can be obtained with little deviation from the default discharge depth of the assembled battery even after the cycle. In addition, a lithium ion secondary battery having a large internal resistance change is used for the storage element D, but since one storage element D is used for 10 non-aqueous secondary batteries A, the assembled battery The change in internal resistance as a battery is also suppressed.

  Therefore, the assembled battery according to the present invention has a stable and high output regardless of the charge / discharge depth, and the internal resistance detection is performed by the power storage element D having a large internal resistance change, and thus the non-aqueous secondary battery having a flat internal resistance change. Even when A is used as the main component, the end stage of charging / discharging can be accurately detected, the deviation of the charging / discharging depth is small, and overcharge and overdischarge are effectively prevented. The assembled battery-9 uses a storage element D having a capacity larger than the capacity of the non-aqueous secondary battery A, but a predetermined amount of electricity is precharged to adjust the discharge depth. When the battery is charged / discharged, there is little voltage deviation, and complete discharge of the electricity storage element D is prevented. Therefore, an assembled battery with reduced deterioration and small deviation in charge / discharge depth can be obtained.

It is the schematic which shows an example of the assembled battery of this invention typically. It is a characteristic view which shows an example of the relationship between the depth of discharge in each unit cell of the non-aqueous secondary battery A of this invention, and the electrical storage element B, and a voltage, (a) is lithium ion with both the non-aqueous secondary battery A and the electrical storage element B When a secondary battery is used, (b) is a battery pack of (a) and the battery element B is precharged, (c) is a non-aqueous secondary battery A as a lithium ion secondary battery, and a battery element B This is a case where an electric double layer capacitor is used. It is a circuit diagram which shows an example of the power supply system of this invention. It is a characteristic view which shows an example of the relationship between the depth of discharge in each cell of the non-aqueous secondary battery A and the electrical storage element D of this invention, and internal resistance.

Explanation of symbols

11 assembled battery 12 non-aqueous secondary battery A
13 Storage element B or Storage element D
21 Power Supply System 22 Main Power Supply Unit 23 Monitoring Unit 24 Control Unit

Claims (18)

A battery pack mainly composed of a plurality of non-aqueous secondary batteries A, wherein the plurality of non-aqueous secondary batteries A and a storage element B having at least one non-aqueous electrolyte for voltage detection are connected in series. ,
Wherein the voltage difference between the voltage (V _A2) per single cell in the discharge depth 75% voltage (V _A1) of per cell at 25% depth of discharge in the non-aqueous secondary battery A △ and V _A, the The voltage per unit cell (V _B1 ) at the discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A in the storage element B and the discharge depth corresponding to 75% of the discharge depth of the non-aqueous secondary battery A when the △ V _B voltage difference between the voltage per unit cell (V _B2) at, characterized in that △ V _B of the power storage device B is larger than △ V _a of the non-aqueous secondary battery a Assembled battery. 2. The assembled battery according to claim 1, wherein a battery capacity C _B per unit cell of the power storage element B is larger than a battery capacity C _A per unit cell of the non-aqueous secondary battery A. 3.   The assembled battery according to claim 1, wherein the storage element B is an electric double layer capacitor.   The assembled battery according to claim 1, wherein the power storage element B is a non-aqueous secondary battery.   The negative electrode of the non-aqueous secondary battery A contains a graphite-based carbon material as a negative electrode active material, and the negative electrode of the electricity storage element B is at least one selected from amorphous carbon, an alloy, and a metal oxide as a negative electrode active material. The assembled battery according to claim 4, comprising a seed material. The positive electrode of the non-aqueous secondary battery A contains at least one selected from an iron phosphate compound and nickel manganese spinel oxide as a positive electrode active material, and the positive electrode of the electricity storage element B has LiMO ₂ ( 5. The assembled battery according to claim 4, wherein M is a lithium oxide represented by the following formula: M is at least one selected from the group consisting of Ni, Co, Mn, Al, and Mg. An assembled battery in which a plurality of non-aqueous secondary batteries A are mainly used, and the plurality of non-aqueous secondary batteries A and a storage element D having at least one non-aqueous electrolyte for detecting internal resistance are connected in series. Te, wherein the non-aqueous internal resistance per cell of 25% depth of discharge of the secondary battery a (R _A1) the difference of △ R _a of the internal resistance per unit cell in the discharge depth 75% (R _A2) And the internal resistance (R _D1 ) per unit cell at a discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A and 75% of the discharge depth of the non-aqueous secondary battery A in the electricity storage element D. the difference between the internal resistance per cell in the discharge depth corresponding (R _D2) △ when the R _D, it △ R _D of the electric device D is greater than the △ R _a of the non-aqueous secondary battery a A battery pack characterized by. Assembled battery according to claim 7, wherein the battery capacity C _D per unit cell of the electric device D is larger than the battery capacity C _A per unit cell of the non-aqueous secondary battery A.   The assembled battery according to claim 7, wherein the storage element D is a non-aqueous secondary battery.   The negative electrode of the non-aqueous secondary battery A contains a graphite-based carbon material as a negative electrode active material, and the negative electrode of the electricity storage element D is at least one selected from amorphous carbon, an alloy, and a metal oxide as a negative electrode active material. The assembled battery according to claim 9, comprising a seed material. The positive electrode of the non-aqueous secondary battery A contains at least one selected from an iron phosphate compound and a nickel manganese spinel oxide as a positive electrode active material, and the positive electrode of the electricity storage element D has LiMO ₂ ( Wherein M is at least one selected from the group consisting of Ni, Co, Mn, Al, and Mg).   A power supply system provided with the assembled battery of any one of Claims 1-11. A plurality of non-aqueous secondary batteries A as a main body, the plurality of non-aqueous secondary batteries A and a storage element B having at least one non-aqueous electrolyte for voltage detection are connected in series, and the non-aqueous secondary battery the voltage difference between the voltage (V _A2) per single cell in the discharge depth 75% voltage (V _A1) of per cell at 25% depth of discharge of the secondary battery a was △ V _a, the power storage device B The voltage per unit cell (V _B1 ) at a discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A and a single discharge depth corresponding to 75% of the discharge depth of the non-aqueous secondary battery A in FIG. when the voltage difference between the voltage (V _B2) per cell △ and V _B, the △ V _B of the storage element B is greater than the △ V _a nonaqueous secondary battery a, and a single of said power storage device B battery capacity C _B per cell per unit cell of the non-aqueous secondary battery a _A method for producing a battery pack having a larger battery capacity CA than
Before connecting the non-aqueous secondary battery A and the electricity storage element B, the electricity storage element B is precharged. The amount of charge of the preliminary charging is an electric quantity equal to or less than a capacity difference between a battery capacity C _B per unit cell of the electricity storage element B and a battery capacity C _A per unit cell of the non-aqueous secondary battery A. The method for producing an assembled battery according to claim 13. The amount of charge of the preliminary charging is about half of the capacity difference between the battery capacity C _B per unit cell of the electricity storage element B and the battery capacity C _A per unit cell of the non-aqueous secondary battery A. The method for producing an assembled battery according to claim 13. A plurality of non-aqueous secondary batteries A are mainly used, and the plurality of non-aqueous secondary batteries A and a storage element D having at least one non-aqueous electrolyte for detecting internal resistance are connected in series. the difference in the internal resistance per cell in the discharge depth 75% internal resistance (R _A1) per unit cell of 25% depth of discharge in aqueous secondary battery a and (R _A2) △ and R _a, the power storage The internal resistance (R _D1 ) per unit cell at the discharge depth corresponding to 25% of the discharge depth of the non-aqueous secondary battery A in the element D and the discharge depth corresponding to 75% of the discharge depth of the non-aqueous secondary battery A when the difference of △ R _D of the internal resistance per cell (R _D2) at, △ R _D of the electric device D is greater than the △ R _a of the non-aqueous secondary battery a, and the accumulator wherein the battery capacity C _D per unit cell of the element D nonaqueous secondary battery A method for producing a battery pack having a battery capacity C _A larger than the battery capacity C _A per cell of the pond A,
Before connecting the non-aqueous secondary battery A and the storage element D, the storage element D is pre-charged, and the assembled battery manufacturing method is characterized in that: Said charge amount of pre-charge, a quantity of electricity within the capacity difference between the battery capacitance C _A of the per cell of the battery capacity C _D and the non-aqueous secondary battery A per unit cell of the electric storage device D The method for producing an assembled battery according to claim 16. Wherein the charge amount of the pre-charging is about half the capacity difference between the battery capacitance C _A of the per cell of the battery capacity C _D and the non-aqueous secondary battery A per unit cell of the electric storage device D The method for producing an assembled battery according to claim 16.

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