ABSTRACT
Abstract
A storage battery system includes a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions, a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, and a controller configured to intermittently connect the module A to the module B to intermittently supply power from the module A to the module B to set a charge state and a discharge depth of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the module B at least from an outside.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2006-163668, filed Jun. 13, 2006, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a storage battery system suitable for, for example, vehicles, bicycles, trams, elevators, aerogenerators and emergency power supplies, etc., which aim to enhance energy efficiency, and also relates to an on-vehicle power supply system and vehicle provided with such a storage battery system.
2. Description of the Related Art
In recent years, hybrid vehicles, bicycles, trams, elevators and aerogenerators, etc., which are provided with a battery, have been proposed, and some of them have been put into practice, to effectively use energy, in particular, regenerative energy as environmental measures. Secondary batteries, which have been proposed as backup power supplies for an emergency, such as a blackout, and have been put to into practice and installed in vehicles so far, include, for example, lead storage batteries and nickel hydride batteries.
However, nickel hydride batteries installed in hybrid vehicles, for example, have the problem that they suddenly generate heat during high-power outputting or fast charging (regenerative charging), and their thermal degradation is very conspicuous. Furthermore, lead storage batteries used as emergency power supplies have a low weight energy density and hence heavy weight, therefore, involve constraints on their installation place.
Hybrid vehicles using a large-capacity capacitor have now been developed. Compared to secondary batteries, capacitors can accumulate high power instantly, but have a very small electric capacity and hence cannot be made compact.
To solve the above problems, JPA KOKAI No. 2003-134689, for example, has proposed a high-power lithium ion battery. While lithium ion batteries can generate high voltage and be made light, and hence have a high energy density, they use a carbon material as the material of their negative electrodes. Accordingly, their cycle lives will degrade if fast charging, such as energy regeneration, is performed. This being so, when low power is input to the batteries, they cannot efficiently accumulate regenerative energy. Further, if lithium ion batteries are made into high-power ones, their inherent high energy density is significantly reduced to thereby reduce their discharge capacity. Accordingly, the travel distance of, for example, electric vehicles is inevitably shortened. Furthermore, for hybrid vehicles, there is a demand for enhancing the energy regenerative performance during braking and the acceleration performance, and also a demand for increasing the travel distance during motor driving (EV driving). However, it is difficult to satisfy both the enhancement of energy regenerative performance and acceleration performance, and the traveling performance during motor driving (EV driving).
JP-A 2004-289892(Kokai) has proposed a hybrid vehicle with a storage battery system as an on-vehicle power supply. The storage battery system includes main and sub battery modules. The sub battery module accumulates regenerative current supplied by a motor or dynamo, and the main battery module is charged with the power accumulated by the sub battery module. However, in this storage battery system, the active material of the negative electrode is low in the rate of occluding and discharging ions, and hence efficient charging cannot be achieved during fast charging, such as regenerative charging.
BRIEF SUMMARY OF THE INVENTION
It is an object of the invention to provide a long-life storage battery system capable of efficient charging during fast charging, such as regenerative charging, and capable of discharging for a long time during a low-load operation, and also to provide an on-vehicle power supply system and vehicle provided with such a storage battery system, and a charging method for such a storage battery system.
In accordance with a first aspect of the invention, there is provided a storage battery system comprising: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions; and a controller configured to intermittently connect the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the battery module B at least from an external source.
In accordance with a second aspect of the invention, there is provided an on-vehicle power supply system comprising: a storage battery system; and a controller, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, wherein the controller intermittently connects the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the storage battery system at least from a motor or dynamo installed in a vehicle.
In accordance with a third aspect of the invention, there is provided an on-vehicle power supply system comprising: a storage battery system; and a controller, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, wherein when power is supplied to the storage battery system from a motor or dynamo installed in a vehicle, the controller intermittently causes the power from the motor or dynamo to be supplied to the battery module B, and causes the battery module A to supply power to the motor, the power from the battery module A being lower than the power supplied to the battery module B.
In accordance with a fourth aspect of the invention, there is provided a vehicle provided with one of the above-described on-vehicle power supply systems.
In accordance with a fifth aspect of the invention, there is provided a method of charging a storage battery system, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, the method comprising: intermittently connecting the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the battery module B at least from an outside.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a schematic plan view illustrating the states of a storage battery system and on-vehicle power supply system according to the invention, assumed during the stop of a motor/dynamo;
FIG. 2 is a schematic plan view illustrating the states of the storage battery system and on-vehicle power supply system according to the invention, assumed during the operation of the motor/dynamo;
FIG. 3 is a perspective view partly broken, illustrating a unit cell included in a battery module;
FIG. 4 is a block diagram illustrating in detail the relationship between the battery module and a battery control unit;
FIG. 5 is an exploded perspective view illustrating a battery pack for use in storage battery systems according to first and second embodiments;
FIG. 6 is a block diagram illustrating the electrical circuits of the battery pack of FIG. 5 ;
FIG. 7 is a graph illustrating battery-voltage/SOC characteristic curves unique to a battery module A and battery module B;
FIG. 8 is a perspective view partly broken, illustrating a flat nonaqueous electrolyte second battery, for use in the battery pack of FIG. 5 , according to another embodiment;
FIG. 9 is an enlarged sectional view of the IX portion of FIG. 8 ;
FIG. 10 is a schematic view showing the bottom of a hybrid vehicle, along with a storage battery system of the invention incorporated in the vehicle;
FIG. 11 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with the storage battery system of the invention incorporated in the vehicle;
FIG. 12 is a schematic view showing the bottom of a hybrid vehicle, along with another storage battery system of the invention incorporated in the vehicle;
FIG. 13 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with said another storage battery system of the invention incorporated in the vehicle;
FIG. 14 is a schematic view showing the bottom of a hybrid vehicle, along with yet another storage battery system of the invention incorporated in the vehicle; and
FIG. 15 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with said yet another storage battery system of the invention incorporated in the vehicle.
DETAILED DESCRIPTION OF THE INVENTION
Preferable embodiments of the invention will be described with reference to the accompanying drawings.
In a storage battery system 1 of the invention, in a first nonaqueous electrolyte battery 6 included in a battery module A, its negative electrode is formed of an active material having an average grain size of 2 μm or more and capable of occluding a large number of lithium ions. Therefore, the battery 6 has a low lithium-ion occluding/discharging rate, but can store a large number of lithium ions. This being so, if the battery 6 serves as the main battery module of the storage battery system 1 of the invention under a low-load driving condition, the storage battery system 1 can operate for a long time.
On the other hand, a second nonaqueous electrolyte battery 7 included in a battery module B is set at an electrical potential of 0.4V (vs.Li/Li) or more for occluding lithium ions. Therefore, the battery 7 has a low energy density, but deposition of lithium metal does not easily occur during fast charging. Further, since the active material of the negative electrode of the battery 7 has an average grain size of primary particles of 1 μm or less, the lithium ion occlusion/discharge rate of the battery 7 is high. Accordingly, if the battery 7 serves as the main power supply of the storage battery system 1 of the invention, the storage battery system 1 exhibits high output/input performance under a driving condition that requires high output power or during power regeneration that requires high input power.
When no power is supplied from the outside to the storage battery system 1 (e.g., when the motor/dynamo of an on-vehicle supply power system is stopped), a controller 4 causes the battery modules A and B to be intermittently connected and to intermittently supply power from the battery module A to the battery module B. As a result, the SOC and DOD of the second nonaqueous electrolyte battery 7 are adjusted to an appropriate range of 10 to 90%, with the result that high output/input performance can be maintained and hence the cycle life of the battery module B can be extended. Namely, by intermittently supplying power to the battery module B, the battery module B can be set to an appropriate charge-state range, thereby suppressing an increase in the resistance of the battery module B in a long inoperative state, and reliably maintaining the high output/input performance over a long period.
Defined here the âintermittent power supplyâ is a power supply in which the electrically disconnected state (rest state) of the battery modules
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2006-163668, filed Jun. 13, 2006, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a storage battery system suitable for, for example, vehicles, bicycles, trams, elevators, aerogenerators and emergency power supplies, etc., which aim to enhance energy efficiency, and also relates to an on-vehicle power supply system and vehicle provided with such a storage battery system.
2. Description of the Related Art
In recent years, hybrid vehicles, bicycles, trams, elevators and aerogenerators, etc., which are provided with a battery, have been proposed, and some of them have been put into practice, to effectively use energy, in particular, regenerative energy as environmental measures. Secondary batteries, which have been proposed as backup power supplies for an emergency, such as a blackout, and have been put to into practice and installed in vehicles so far, include, for example, lead storage batteries and nickel hydride batteries.
However, nickel hydride batteries installed in hybrid vehicles, for example, have the problem that they suddenly generate heat during high-power outputting or fast charging (regenerative charging), and their thermal degradation is very conspicuous. Furthermore, lead storage batteries used as emergency power supplies have a low weight energy density and hence heavy weight, therefore, involve constraints on their installation place.
Hybrid vehicles using a large-capacity capacitor have now been developed. Compared to secondary batteries, capacitors can accumulate high power instantly, but have a very small electric capacity and hence cannot be made compact.
To solve the above problems, JPA KOKAI No. 2003-134689, for example, has proposed a high-power lithium ion battery. While lithium ion batteries can generate high voltage and be made light, and hence have a high energy density, they use a carbon material as the material of their negative electrodes. Accordingly, their cycle lives will degrade if fast charging, such as energy regeneration, is performed. This being so, when low power is input to the batteries, they cannot efficiently accumulate regenerative energy. Further, if lithium ion batteries are made into high-power ones, their inherent high energy density is significantly reduced to thereby reduce their discharge capacity. Accordingly, the travel distance of, for example, electric vehicles is inevitably shortened. Furthermore, for hybrid vehicles, there is a demand for enhancing the energy regenerative performance during braking and the acceleration performance, and also a demand for increasing the travel distance during motor driving (EV driving). However, it is difficult to satisfy both the enhancement of energy regenerative performance and acceleration performance, and the traveling performance during motor driving (EV driving).
JP-A 2004-289892(Kokai) has proposed a hybrid vehicle with a storage battery system as an on-vehicle power supply. The storage battery system includes main and sub battery modules. The sub battery module accumulates regenerative current supplied by a motor or dynamo, and the main battery module is charged with the power accumulated by the sub battery module. However, in this storage battery system, the active material of the negative electrode is low in the rate of occluding and discharging ions, and hence efficient charging cannot be achieved during fast charging, such as regenerative charging.
BRIEF SUMMARY OF THE INVENTION
It is an object of the invention to provide a long-life storage battery system capable of efficient charging during fast charging, such as regenerative charging, and capable of discharging for a long time during a low-load operation, and also to provide an on-vehicle power supply system and vehicle provided with such a storage battery system, and a charging method for such a storage battery system.
In accordance with a first aspect of the invention, there is provided a storage battery system comprising: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions; and a controller configured to intermittently connect the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the battery module B at least from an external source.
In accordance with a second aspect of the invention, there is provided an on-vehicle power supply system comprising: a storage battery system; and a controller, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, wherein the controller intermittently connects the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the storage battery system at least from a motor or dynamo installed in a vehicle.
In accordance with a third aspect of the invention, there is provided an on-vehicle power supply system comprising: a storage battery system; and a controller, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, wherein when power is supplied to the storage battery system from a motor or dynamo installed in a vehicle, the controller intermittently causes the power from the motor or dynamo to be supplied to the battery module B, and causes the battery module A to supply power to the motor, the power from the battery module A being lower than the power supplied to the battery module B.
In accordance with a fourth aspect of the invention, there is provided a vehicle provided with one of the above-described on-vehicle power supply systems.
In accordance with a fifth aspect of the invention, there is provided a method of charging a storage battery system, the storage battery system including: a battery module A with a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more and is used to occlude and discharge lithium ions; and a battery module B with a second nonaqueous electrolyte battery set at a lithium-ion-occluding potential of 0.4V (vs.Li/Li) or more, and including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is used to occlude lithium ions, the method comprising: intermittently connecting the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B to set state of charge (SOC) and a depth of discharge (DOD) of the second nonaqueous electrolyte battery within a range of 10 to 90%, when no power is supplied to the battery module B at least from an outside.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a schematic plan view illustrating the states of a storage battery system and on-vehicle power supply system according to the invention, assumed during the stop of a motor/dynamo;
FIG. 2 is a schematic plan view illustrating the states of the storage battery system and on-vehicle power supply system according to the invention, assumed during the operation of the motor/dynamo;
FIG. 3 is a perspective view partly broken, illustrating a unit cell included in a battery module;
FIG. 4 is a block diagram illustrating in detail the relationship between the battery module and a battery control unit;
FIG. 5 is an exploded perspective view illustrating a battery pack for use in storage battery systems according to first and second embodiments;
FIG. 6 is a block diagram illustrating the electrical circuits of the battery pack of FIG. 5 ;
FIG. 7 is a graph illustrating battery-voltage/SOC characteristic curves unique to a battery module A and battery module B;
FIG. 8 is a perspective view partly broken, illustrating a flat nonaqueous electrolyte second battery, for use in the battery pack of FIG. 5 , according to another embodiment;
FIG. 9 is an enlarged sectional view of the IX portion of FIG. 8 ;
FIG. 10 is a schematic view showing the bottom of a hybrid vehicle, along with a storage battery system of the invention incorporated in the vehicle;
FIG. 11 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with the storage battery system of the invention incorporated in the vehicle;
FIG. 12 is a schematic view showing the bottom of a hybrid vehicle, along with another storage battery system of the invention incorporated in the vehicle;
FIG. 13 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with said another storage battery system of the invention incorporated in the vehicle;
FIG. 14 is a schematic view showing the bottom of a hybrid vehicle, along with yet another storage battery system of the invention incorporated in the vehicle; and
FIG. 15 is a schematic view showing the bottom of a plug-in-type hybrid vehicle, along with said yet another storage battery system of the invention incorporated in the vehicle.
DETAILED DESCRIPTION OF THE INVENTION
Preferable embodiments of the invention will be described with reference to the accompanying drawings.
In a storage battery system 1 of the invention, in a first nonaqueous electrolyte battery 6 included in a battery module A, its negative electrode is formed of an active material having an average grain size of 2 μm or more and capable of occluding a large number of lithium ions. Therefore, the battery 6 has a low lithium-ion occluding/discharging rate, but can store a large number of lithium ions. This being so, if the battery 6 serves as the main battery module of the storage battery system 1 of the invention under a low-load driving condition, the storage battery system 1 can operate for a long time.
On the other hand, a second nonaqueous electrolyte battery 7 included in a battery module B is set at an electrical potential of 0.4V (vs.Li/Li) or more for occluding lithium ions. Therefore, the battery 7 has a low energy density, but deposition of lithium metal does not easily occur during fast charging. Further, since the active material of the negative electrode of the battery 7 has an average grain size of primary particles of 1 μm or less, the lithium ion occlusion/discharge rate of the battery 7 is high. Accordingly, if the battery 7 serves as the main power supply of the storage battery system 1 of the invention, the storage battery system 1 exhibits high output/input performance under a driving condition that requires high output power or during power regeneration that requires high input power.
When no power is supplied from the outside to the storage battery system 1 (e.g., when the motor/dynamo of an on-vehicle supply power system is stopped), a controller 4 causes the battery modules A and B to be intermittently connected and to intermittently supply power from the battery module A to the battery module B. As a result, the SOC and DOD of the second nonaqueous electrolyte battery 7 are adjusted to an appropriate range of 10 to 90%, with the result that high output/input performance can be maintained and hence the cycle life of the battery module B can be extended. Namely, by intermittently supplying power to the battery module B, the battery module B can be set to an appropriate charge-state range, thereby suppressing an increase in the resistance of the battery module B in a long inoperative state, and reliably maintaining the high output/input performance over a long period.
Defined here the âintermittent power supplyâ is a power supply in which the electrically disconnected state (rest state) of the battery modules A and B and the electrically connected state (charging state) thereof are switched in accordance with the SOC of the battery module B, instead of always electrically connecting the battery modules A and B, thereby adjusting the length of the electrically disconnected period (rest period). For instance, when the SOC of the battery module B is high, the electrically disconnected period is lengthened, whereas when it is low, the electrically disconnected period is shortened. It is desirable to perform charging by constant voltage control from the battery module A to the battery module B. This power supply scheme enables charging to be finished in a short time.
In contrast, if power is continuously supplied without the electrically disconnected period, the internal resistance of the battery module B is gradually increased, thereby degrading the output/input performance. This is because electrolytic solution is subjected to oxidation decomposition reaction on the surface of the positive electrode, whereby an oxide film of high resistance grows on the positive electrode.
It is preferable that the battery modules A and B are electrically connected 1 to 60 times per 30 days to supply power from the battery module A to the battery module B so that the SOC of the battery module B is adjusted to the range of 10 to 90%. Namely, it is sufficient if electrical connection is executed a preset number of times per 30 days to intermittently supply power from the battery module A to the battery module B (i.e., to intermittently charge the battery module B) by the amount of electricity self-discharged from the battery module B, said preset number falling within a range of 1 to 60 times. If the battery modules A and B are electrically connected at a frequency higher than the appropriate range, the electricity storage life of the battery module B is reduced, since oxidation decomposition of electrolytic solution occurs on the positive electrode to thereby increase the resistance of the positive electrode and significantly reduce the output/input performance. A more preferable frequency of electrical connection is 10 to 40 times per 30 days. In contrast, if the battery modules A and B are electrically connected at a frequency lower than the appropriate range, the amount of self discharge is increased and insufficient power supplement may occur.
A more preferable range of charge state is 20 to 80%. If the charge state is kept in this range, the resistance of the battery can be further reduced, and hence the output/input performance of the storage battery system can be maintained at high level.
It is preferable to supply power from the battery module B to the battery module A (i.e., charge the battery module A) when the charge state of the battery module B falls within the range of 50 to 100%. By supplying power to the battery module A when the charge state of the battery module B falls within the range of 50 to 100%, the output/input performance of the storage battery system can be maintained at high level. Namely, the charge state of the battery module B is prevented from excessive increase. A more preferable range of charge state is 60 to 80%. It is also preferable to employ constant-current/constant-voltage control as a scheme for supplying power from the battery module B to the battery module A.
For nonaqueous electrolyte batteries, there are various charging schemes, such as constant current charging, constant voltage charging, and constant current and constant voltage charging, etc. The âconstant current charging (CC charging)â means a charging scheme utilizing a particular current. The âconstant voltage charging (CV charging)â means a charging scheme utilizing a particular voltage. Similarly, the âconstant current and constant voltage charging (CCCV charging)â means a charging scheme acquired by combining CC charging and CV charging. During CCCV charging, firstly, CC charging is performed until a particular voltage is reached, and then CV charging is performed for a preset period using the particular voltage. In the invention, it is desirable to employ CV charging when power is supplied from the battery module A to the battery module B. Since the battery module B serves as a main power supply when device driving that requires high output or power regeneration that requires high input is performed, it is necessary to perform charging at a high charging rate in a short time. In contrast, to supply power from the battery module B to the battery module A, it is desirable to employ CCCV charging. This is because the battery module A serves as a main power supply under a low-load driving condition, and hence should be charged safely so as not to degrade its cycle life.
In an on-vehicle power supply system, when power is supplied from a motor or dynamo 5 to the storage battery system, the battery module B is supplied with power from the motor/ dynamo 5 , and the battery module A supplies power lower than the first-mentioned one to the motor 5 , as shown in FIG. 2 . The supply of power to the battery module B is performed to efficiently accumulate braking energy therein. Depending upon whether the vehicle performs accelerated traveling or constant traveling, the level (W) of supplied power is varied. This is because the level of power supplied from the battery module A to the motor 5 during constant traveling is lower than that of power supplied to the battery module B during acceleration.
It is preferable that the active material of the negative electrode of the second nonaqueous electrolyte battery (battery module B) contains a metal oxide containing titanium. Further, it is preferable that the metal oxide containing titanium contains a spinel-type lithium titanium oxide. The active material of the negative electrode of the second nonaqueous electrolyte battery, which is set to a potential of 0.4V (vs.Li/Li) or more for occluding lithium ions with an average grain size of primary particles of 1 μm or less, preferably contains a metal oxide containing titanium, and more preferably contains a spinel-type lithium titanium oxide. The second nonaqueous electrolyte battery exhibits high output/input performance by virtue of fine primary particles with the average grain size of 1 μm or less, and also exhibits an excellent long cycle-life performance since the degree of decomposition of electrolytic solution due to charge/discharge cycle or a change in electrode volume is very small.
Further, it is preferable that the active material of the negative electrode of the first nonaqueous electrolyte battery (battery module A) contains a carbon material with an average grain size of 1 μm or more, and a lithium alloy and metal alloy for occluding and discharging lithium ions. It is more preferable that the carbon material contained in the first nonaqueous electrolyte battery contains graphite particles acquired using natural graphite as a raw material. Since thus, the active material of the negative electrode of the first nonaqueous electrolyte battery (battery module A) contains a carbon material with an average grain size of 1 μm or more, a lithium alloy and a metal alloy, the rate of occluding/discharging lithium ions is low, and a large amount of lithium ions can be extracted during a low-load operation. Further, since the potential for occluding lithium ions is low, the first nonaqueous electrolyte battery can generate high voltage and hence have a higher energy density than the second nonaqueous electrolyte battery (battery module B). It is more preferable that the carbon material contains graphite particles acquired using natural graphite as a raw material.
FIG. 7 is a graph illustrating battery-voltage/SOC characteristic curves unique to a battery module A and battery module B. In FIG. 7 , curve (broken line) A indicates the characteristic of the battery module A, and curve (solid line) B indicates the characteristic of the battery module B. As can be understood from FIG. 7 , the battery module A has a characteristic suitable for CCCV charging. Namely, the battery module A is firstly charged with a particular current (CC charging). When the voltage of the cell A reaches a particular voltage Emax, CC charging is switched to CV charging, and CV charging is executed for a preset period with the battery voltage kept Emax. The charging period is controlled by the built-in timer of the controller 4 . The voltage Vmax is a maximum value within the range in which the battery module A is prevented from excessive charging. On the other hand, the battery module B has a characteristic suitable for CC or CV charging. Namely, the battery module B is charged with the particular current (CC charging), and reaches a voltage Ee when the charging is finished ( SOC 100%). The final voltage Ee of the battery module B is, for example, 238V.
Various embodiments of the invention will be described in detail with reference to the accompanying drawings.
First Embodiment
As shown in FIGS. 1 and 2 , the storage battery system 1 of the first embodiment comprises a booster mechanism 2 , battery modules A and B connected to the booster mechanism 2 , and a battery control unit (BMU) 4 connected to the battery modules A and B. The battery module B has a module, in which a plurality of single cells formed of thin nonaqueous electrolyte secondary batteries 7 are connected parallel to each other or in series. The battery module A is intermittently connected to the battery module B parallel to each other via a controller 8 , and controls the amounts of current input to and output from the battery module B. The controller B contains a DC/DC converter, and performs constant voltage control to enable power to be supplied from the battery module A to the battery module B.
FIG. 3 shows an example of a unit cell 21 as a nonaqueous electrolyte battery. An electrode group 11 has a flat, spiral structure formed of a positive electrode 12 , negative electrode 13 and separator 14 interposed therebetween. The electrode group 11 is formed by winding the positive electrode 12 and negative electrode 13 with the separator 14 interposed therebetween, and then subjecting the resultant structure to thermal pressing. Alternatively, the positive electrode 12 , negative electrode 13 and separator 14 may be formed integral using an adhesive polymer. A band-shaped positive terminal 15 is electrically connected to the positive electrode 12 . Similarly, a band-shaped negative terminal 16 is electrically connected to the negative electrode 13 . The electrode group 11 is contained in a laminate- film container 17 with the ends of the positive and negative terminals
15 and 16 made to protrude from the container. The laminate film container 17 is sealed by a heat seal.
As shown in FIG. 4 , the battery control unit (BMU) 4 comprises temperature sensors
61 a and 61 b for measuring the temperatures of the battery modules A and B, respectively, voltmeters
63 a and 63 b for measuring the voltages of the battery modules A and B, respectively, ammeters
62 a and 62 b for measuring the currents of the battery modules A and B, respectively, a charge/ discharge control circuit 40 , charge interruption circuit 41 and discharge interruption circuit 42 . The temperature sensors 61 and 62 may be formed of thermo couples or thermistors.
The charge/ discharge control circuit 40 receives measurement signals from the temperature sensors
61 a and 61 b , voltmeters
63 a and 63 b and ammeters
62 a and 62 b . Based on the input signals the control circuit 40 computes the present charge capacity, and supplies signals to the charge interruption circuit 41 and discharge interruption circuit 42 for setting a certain state of charge (SOC), thereby controlling the charge/discharge of the nonaqueous electrolyte batteries
6 and 7 of the battery modules A and B.
The storage battery system 1 constructed as above can be connected to a DC motor/ dynamo 5 as an external load incorporated in, for example, a hybrid vehicle or electric vehicle. In this case, the dynamo connected to the DC motor is connected to the booster mechanism 2 of the storage battery system. The booster mechanism 2 serves as a charger for supplying regenerative power at least to the battery module B. On the other hand, the DC motor 5 is connected to the BMU 4 of the storage battery system 1 . As a result, the output of the battery modules A and B supplied to the DC motor can be controlled in accordance with signals from the charge/ discharge control circuit 40 and discharge interruption circuit 42 . Further, the controller 8 can control the battery module B to supply power from the battery module B to the battery module A to charge it when the state of charge (SOC) of the battery module B falls within the range of 50 to 100%. Further, the battery module A can be directly charged by an external charger 71 and/or power supply 73 as in on-vehicle power supply systems 50 A to 50 F incorporated in the plug-in hybrid vehicles shown in FIGS. 11 , 13 and 15 .
It is preferable to intermittently supply power from the battery module A to the battery module B by constant-voltage control, to thereby adjust the SOC of the battery module B within a range of 10 to 90%, and more preferably, a range of 40 to 60%. In particular, when the on-vehicle power supply system is stopped (for example, when the motor and dynamo are stopped during long-time parking of the vehicle), the battery module A charges the battery module B by the amount of electricity corresponding to the self-discharge of the battery module B. Further, when the battery module B instantly discharges high power to the outside (during, for example, acceleration of the vehicle), and the SOC is suddenly reduced to 40% or less, the battery module A supplies power to the battery module B to set the SOC of the battery module B within the range of 40 to 60%. At this time, it is preferable that the supply of power is performed rapidly using constant-voltage control. More specifically, when the state of charge (SOC) of the battery module B drops to 40% or lower, the MBU 4 operates to have a power supply from the battery module A to the battery module B by the constant-voltage control. It should be noted that various types of external power sources can be connected to the battery module B to supply power thereto. The battery module B is provided with a power supply directly from an external power source. Further, the battery module A is provided with a power supply from the external power source via the battery module B.
Although the storage battery systems and on-vehicle power supply systems shown in FIGS. 1 and 2 do not incorporate a cooling fan, a cooling fan may be employed to cool the battery modules. Further, an AC motor may be used instead of the DC motor. In the case of using an AC motor, a rectifier is needed.
A description will now be given of the negative and positive electrodes, separator, nonaqueous electrolyte and container of each nonaqueous electrolyte battery.
1) Negative Electrode
A negative electrode comprises a negative collector, and a negative-electrode layer provided on one or both sides of the collector and containing a negative-electrode active material, conductive agent and binding agent.
It is desirable to use, as the negative-electrode active material of each second nonaqueous electrolyte battery 7 of the battery module B, a metal oxide, metal sulfide, metal nitride or metal alloy, which have an average grain size of primary particles of 1 μm or less and can occlude lithium ions within a range of 0.4V to 3V (vs.Li/Li+). In particular, it is preferable to use a negative-electrode material containing a lithium titanium complex oxide. As the lithium titanium complex oxide, lithium titanate (e.g., spinel-type Li 4+X Ti 5 O 12 , x: â1â¦xâ¦3, and preferably, 0<x<1) can be used. In view of cycle life, lithium titanate is preferable. This is because the lithium occluding potential of lithium titanate is about 1.5V, and is electrochemically very stable material with respect to an aluminum foil collector or aluminum alloy foil collector.
As well as the above-mentioned spinel-type lithium titanate, a ramsdellite-type lithium titanate, such as Li 2+X Ti 3 O 7 (x: â1â¦xâ¦3), can be used. Hereinafter, the spinel-type lithium titanate and ramsdellite-type lithium titanate will be referred to as âlithium titanium oxides.â Lithium titanium complex oxides include, as well as lithium titanium oxides, titanium-based oxides that do not contain lithium. Lithium titanium oxides include, for example, a metal complex oxide containing at least one element selected from the group of TiO 2 , Ti, P, V, Sn, Cu, Ni and Fe. It is preferable that TiO 2 is of an anatase type and has low crystalline properties acquired at a thermal treatment temperature of 300 to 500° C. As a metal complex oxide containing at least one element selected from the group of Ti, P, V, Sn, Cu, Ni and Fe, TiO 2 âP 2 O 5 , TiO 2 âV 2 O 5 , TiO 2 âP 2 O 5 âSnO 2 , and TiO 2 âP 2 O 5 âMeO (Me is at least one metal selected from the group consisting of Cu, Ni and Fe), etc., can be exemplified. It is preferable that the metal complex oxide has low crystalline properties, and has a microstructure in which a crystalline phase and amorphous phase are mixed, or only an amorphous phase exists. By virtue of this microstructure, the cycle performance can be significantly enhanced. In particular, a metal complex oxide containing a lithium titanium oxide and at least one element selected from the group of Ti, P, V, Sn, Cu, Ni and Fe is preferable.
The negative-electrode active material may contain a material other than a lithium titanium complex oxide. This material is, for example, a carbonaceous material that can occlude and discharge lithium.
The average grain size of the primary particles of the negative-electrode material is 1 μm or less. The use of a negative-electrode material with an average grain size of 1 μm or less enhances the cycle performance. In particular, this effect is conspicuous during rapid charging and high-output discharging. Concerning, for example, a negative-electrode for occluding and discharging lithium ions, the reason why the effect is conspicuous is that the finer, the grain size, the shorter the diffusion distances of lithium ions in the active material and the greater the specific surface of each particle. More preferably, the average grain size of the negative-electrode material is 0.3 μm or less. However, when the average grain size of the negative-electrode material is small, aggregation of particles may easily occur, which may involve a reduction in the uniformity of the particle size of the negative-electrode active material. In light of this, it is desirable to set its lower limit to 0.001 μm.
Concerning primary particles of a negative-electrode active material with an average grain size of 1 μm or less, it is desirable to subject a row material for the active material to synthesis to thereby prepare, as an active material precursor, powder with a diameter of 1 μm or less. The negative-electrode active material is acquired by crushing up the powder acquired after sintering into 1 μm or less, using a crusher, such as a ball mill or jet mill.
The grain size of primary particles of the negative-electrode active material is measured by a laser-diffraction-type grain-size-distribution measuring apparatus (SALD-300 made by Shimazu Corporation). Firstly, as a pretreatment, a aggregated sample is diffused in the following manner. That is, a sample of about 0.1 g, an interfacial active material and distilled water of 1-2 mL are fed into a beaker and sufficiently agitated. After that, the resultant solution is injected into an agitation vessel, where it is subjected to light-intensity-distribution measurement performed 64 times at intervals of 2 seconds, thereby acquiring grain-size distribution data. Thus, measurement results, such as a grain-size distribution and average grain size of the primary particles, are obtained.
It is preferable that the negative collector is formed of aluminum foil or aluminum alloy foil. It is also preferable that the average crystal grain size of the aluminum foil or aluminum alloy foil is 50 μm or less, and more preferably, 10 μm or less. The smaller the average crystal grain size, the stronger the chemical and physical strengths. However, from the fact that a fine crystal structure is desirable to acquire excellent conductivity, it is desirable to set the lower limit of the average crystal grain size to 0.01 μm.
When the average crystal grain size of the aluminum foil or aluminum alloy foil is set to 50 μm or less, the strength of the negative collector can be significantly increased. The greater the strength of the negative collector, the greater the physical and chemical resistances of the collector, and hence the less the breakage of the collector. In particular, degradation of the collector due to dissolution/corrosion, which is conspicuous in a long excessive-discharge cycle at a high temperature (40° C. and above), can be suppressed to thereby suppress an increase in electrode resistance. Suppression in an increase in electrode resistance reduces the Joule heat, thereby suppressing heat generation by the electrodes.
Further, by virtue of an increase in the strength of the negative collector, it is not broken even when high pressure is exerted thereon. This enhances the capacity density of the negative electrodes.
In general, when pressing the negative electrode, the smaller the average grain size of the negative-electrode active material, the greater the load on the negative collector. If the negative collector is formed of an aluminum foil or aluminum alloy foil with an average crystal grain size of 50 μm or less, it can wear a great pressing force exerted thereon by virtue of the strength of the negative-electrode material with an average grain size of 1 μm or less. As a result, breakage of the negative collector during pressing can be avoided.
Further, since a large number of negative electrodes can be integrated, the thermal conductivity of the electrodes can be enhanced, and hence the heat-releasing property of the electrodes be enhanced. Furthermore, the synergistic effect of the suppression of the heat generation of the battery, and the enhancement of the heat-releasing property of the electrodes result in the suppression of increases in the temperature of the battery.
Aluminum foil or aluminum alloy foil with an average crystal grain size of 50 μm or less is influenced in a complicated manner by many factors, such as their composition, impurities, process conditions, thermal treatment history, and heating and cooling conditions of annealing. Accordingly, during the manufacturing process, the crystal grain size of the negative collector is adjusted in light of all the above-mentioned factors. The negative collector may be produced using PACAL21 (product name) of Nippon Foil Mig. Co., Ltd.
Specifically, aluminum foil with the average crystal grain size of 50 μm or less can be produced by annealing aluminum foil with an average crystal grain size of 90 μm at 50 to 250° C., and cooling the resultant material to the room temperature.
The average crystal grain size of aluminum and an aluminum alloy is measured as follows:
Firstly, the texture of the surface of a negative collector is observed using a metallographic microscope to measure the number ânâ of crystal grains existing in a viewing field of 1 μmÃ1 μm, thereby computing an average crystal grain area S (μm 2 ) using the following equation (1):
S =(1Ã10 6 )/ n ââ(1)
where (1Ã10 6 ) is a viewing field area of 1 μmÃ1 μm (μm 2 ), and n is the number of crystal grains.
An average crystal grain size d (μm) is computed using the acquired average crystal grain area S and the following equation (2):
d =2( S /Ï) 1/2 ââ(2)
Such average-crystal-grain-diameter computation is performed concerning five portions (5 viewing fields), and the average of the resultant values is set as an average crystal grain size. The expected error is about 5%.
It is preferable that the thickness of the negative collector is 20 μm or less, and the purity of aluminum foil is 99.99% or more. It is also preferable that the aluminum alloy contains magnesium, tin, manganese, silicon, etc. In contrast, it is preferable that the amounts of transition metals, such as iron, copper, nickel and chrome, are set to 100 ppm or less.
A carbon material, such as acetylene black, carbon black, coke, carbon fiber or graphite, can be used as a conductive material.
As the binding agent, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine system rubber, butadiene-styrene rubber, etc., can be used.
Concerning the composition ratio of the negative-electrode active material, conductive agent and binding agent, it is preferable to set the negative-electrode active material to 80 to 95 weight %, set the conductive agent to 3 to 18 weight %, and set the binding agent to 2 to 7 weight %.
The negative electrode is produced by, for example, suspending the negative-electrode active material, conductive agent and binding agent in an appropriate solvent, coating an aluminum foil or aluminum alloy foil collector with the suspended solids, drying them and pressing them. The thickness of an active-material layer on one side of the negative collector is preferably 5 to 100 μm, and more preferably, 5 to 50 μm. If the thickness of the active-material layer falls within the range of 5 to 50 μm, the layer exhibits high thermal conductivity during charging/discharging of a large current, and suppresses rapid heat generation.
It is preferable to use, as the negative-electrode active material of the first nonaqueous electrolyte battery 6 (battery module A), a material that occludes and discharges lithium ions with an average grain size of 1 μm or more. As such a material, a lithium metal, lithium alloy or metal compound can be used. It is desirable to convert the negative-electrode active material of the average grain size of 1 μm or more into powder with a diameter of 1 μm or less as an active material precursor. The negative-electrode active material is acquired by crushing up the powder acquired after sintering into 1 μm or less, using a crusher, such as a ball mill or jet mill.
The grain size of the negative-electrode active material is measured by a laser-diffraction-type grain-size-distribution measuring apparatus (SALD-300 made by Shimazu Corporation). Firstly, a sample of about 0.1 g, an interfacial active material and distilled water of 1-2 mL are fed into a beaker and sufficiently agitated. After that, the resultant solution is injected into an agitation vessel, where it is subjected to light-intensity-distribution measurement performed 64 times at intervals of 2 seconds, thereby acquiring grain-size distribution data. Thus, measurement results, such as a grain-size distribution and average grain size, are obtained.
The
CLAIMS
Claims ( 13 )
1. An on-vehicle power supply system comprising: a storage battery system, the storage battery system comprising:
a battery module A comprising a first nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of 2 μm or more;
a battery module B comprising a second nonaqueous electrolyte battery including a negative-electrode material which has an average grain size of primary particles of 1 μm or less and is configured to occlude lithium ions within a range of 0.4V (vs.Li/Li+) or more;
a motor or dynamo configured to supply a power to the battery module B; and
a controller configured to intermittently connect the battery module A to the battery module B to intermittently supply power from the battery module A to the battery module B by repeating cycles of charging the battery module B from the battery module A and non-charging, while setting a state of charge of the second nonaqueous electrolyte battery within a range of 10 to 90%, when the motor or dynamo is stopped,
wherein when power is supplied to the storage battery system from the motor or dynamo, the controller intermittently causes the power from the motor or dynamo to be supplied to the battery module B, and causes the battery module A to supply power to the motor or dynamo, the power from the battery module A being lower than the power supplied to the battery module B.
2. The on-vehicle power supply system according to claim 1 , wherein the controller connects the battery module A to the battery module B a preset number of times per 30 days to supply, the preset number falling within a range of 1 to 60 times, using a constant-voltage control scheme, power from the battery module A to the battery module B to set the state of charge of the second nonaqueous electrolyte battery within the range of 10 to 90%.
3. The on-vehicle power supply system according to claim 1 , wherein the controller causes power to be supplied from the battery module B to the battery module A, using a constant-current control scheme and a constant-voltage control scheme, when the state of charge of the second nonaqueous electrolyte battery falls within a range of 50 to 100%.
4. The on-vehicle power supply system according to claim 1 , further comprising an external power source connected to the battery module B to supply power thereto, wherein the battery module A is provided with the power supply from the external power source via the battery module B.
5. The on-vehicle power supply system according to claim 1 , wherein the negative-electrode material of the second nonaqueous electrolyte battery includes a metal oxide containing titanium.
6. The on-vehicle power supply system according to claim 5 , wherein the metal oxide contains a spinel-type lithium titanium oxide.
7. The on-vehicle power supply system according to claim 1 , wherein the negative-electrode material of the first nonaqueous electrolyte battery contains a carbon material, a lithium alloy and a metal compound.
8. The on-vehicle power supply system according to claim 7 , wherein the carbon material contains graphite powder acquired using natural graphite as a row material.
9. The on-vehicle power supply system according to claim 1 , wherein the controller causes power to be supplied from the battery module A to the battery module B, using a constant-voltage control scheme, when the state of charge of the second nonaqueous electrolyte battery drops to 40% or less.
10. The on-vehicle power supply system according to claim 1 , further comprising an inverter interposed between the motor or dynamo and the battery module B, the motor or dynamo connected to the battery module B to supply power thereto via the inverter, and then to the battery module A from the battery module B.
11. The on-vehicle power supply system according to claim 1 , further comprising a plug connectable to an external power-supply socket, and a built-in charger interposed between the plug and the battery module B, the plug being connected to the power-supply socket to supply external power to the battery module B via the built-in charger, and then to the battery module A from the battery module B.
12. A vehicle comprising the on-vehicle power supply system according to claim 1 .
13. The on-vehicle power supply system according to claim 1 , wherein the controller connects the battery module A to the battery module B 1 to 60 times per 30 days.
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