WO2015025402A1 - リチウムイオン電池の充放電制御方法および充放電制御装置 - Google Patents
リチウムイオン電池の充放電制御方法および充放電制御装置 Download PDFInfo
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- WO2015025402A1 WO2015025402A1 PCT/JP2013/072410 JP2013072410W WO2015025402A1 WO 2015025402 A1 WO2015025402 A1 WO 2015025402A1 JP 2013072410 W JP2013072410 W JP 2013072410W WO 2015025402 A1 WO2015025402 A1 WO 2015025402A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
- G01R31/3828—Arrangements for monitoring battery or accumulator variables, e.g. SoC using current integration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/392—Determining battery ageing or deterioration, e.g. state of health
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a charge / discharge control method and a charge / discharge control device for a lithium ion battery.
- a secondary battery capable of repeatedly charging and discharging electricity is an essential component as a power source (energy source) of such hybrid vehicles and electric vehicles.
- the lithium ion battery is a high energy density secondary battery which has a high operating voltage and can easily obtain a high output. Therefore, as a power source of a hybrid car and an electric car, in recent years, importance is increasing more and more.
- Patent Document 1 discloses that the deterioration of the active material is suppressed by using a binder that has a high coverage with the electrode material and a high adhesion. ing.
- the charge / discharge control method of a lithium ion battery according to the present invention is a charge / discharge control method of a lithium ion battery which has a negative electrode active material and is connected to the charge / discharge control device.
- the battery information on the charge and discharge state of the battery is acquired, the deterioration state of the lithium ion battery is determined based on the battery information, and the voltage range for charge and discharge of the lithium ion battery is changed based on the determination result of the deterioration state.
- the charge / discharge control device controls charge / discharge of a lithium ion battery having a negative electrode active material, and acquires a battery information acquisition unit that acquires battery information regarding the charge / discharge state of the lithium ion battery;
- the voltage range for charging and discharging of the lithium ion battery is determined based on the deterioration state determination unit that determines the deterioration state of the lithium ion battery based on the battery information acquired by the storage unit and the determination result of the deterioration state by the deterioration state determination unit.
- a voltage range changing unit to be changed.
- the cycle characteristics of a lithium ion battery can be effectively improved.
- FIG. 1 is a block diagram showing the configuration of a charge / discharge control device 100 according to an embodiment of the present invention.
- the charge / discharge control device 100 shown in FIG. 1 is a device for controlling charge / discharge of a lithium ion battery 10 (hereinafter simply referred to as a battery 10) which is a secondary battery.
- a state determination unit 13, a voltage range change unit 14, and a control signal transmission unit 15 are functionally included.
- the charge and discharge control device 100 is connected to the battery 10 and the controller 11.
- the battery information acquisition unit 12 uses, as battery information related to the charge / discharge state of the battery 10, information such as the voltage (closed circuit voltage) between the terminals of the battery 10 being charged / discharged, the current flowing through the battery 10, the charge / discharge time of the battery 10 get.
- the battery information acquisition unit 12 can acquire such battery information using, for example, a voltmeter, an ammeter, a timer or the like.
- the battery information acquisition unit 12 outputs each acquired battery information to the deterioration state determination unit 13.
- the deterioration state determination unit 13 determines the deterioration state of the battery 10, that is, the degree of deterioration, based on each piece of battery information acquired by the battery information acquisition unit 12. The determination method of the degradation state of the battery 10 by the degradation state determination unit 13 will be described in detail later.
- the deterioration state determination unit 13 determines the deterioration state of the battery 10
- the deterioration state determination unit 13 outputs the determination result to the voltage range change unit 14.
- the voltage range changing unit 14 changes the voltage range for charging and discharging of the battery 10 based on the determination result of the deterioration state of the battery 10 by the deterioration state determining unit 13. That is, according to the deterioration state of battery 10 with respect to the upper limit voltage (charge upper limit voltage) of battery 10 at the time of charge and the lower limit voltage (discharge lower limit voltage) of battery 10 at the time of discharge. Calculate the values for resetting. The method of changing the voltage range by the voltage range changing unit 14 will also be described in detail later. After calculating the reset value of the charge upper limit voltage and the reset value of the discharge lower limit voltage, the voltage range change unit 14 outputs these to the control signal transmission unit 15 as information indicating the voltage range after the change.
- the control signal transmitting unit 15 transmits, to the controller 11, a control signal for instructing a voltage range after the change. That is, it generates a control signal indicating the reset value of the charge upper limit voltage and the reset value of the discharge lower limit voltage, and outputs the control signal to the controller 11.
- the charge and discharge control device 100 can perform charge and discharge control of the battery 10 using the controller 11 with each configuration as described above.
- the controller 11 controls the energization state of the battery 10 during charging and discharging so that charging and discharging of the battery 10 are performed within the range of preset voltage and current.
- the controller 11 receives the control signal, and based on the received control signal, the charge and discharge of the battery 10 is performed. Change the voltage range. Then, the battery 10 is energized in accordance with the changed voltage range.
- Charge / discharge control device 100 can realize each component as shown in FIG. 1 using, for example, a CPU, a ROM, a RAM, an HDD, and the like. That is, the above-described battery information acquisition unit 12, the deterioration state determination unit 13, and the voltage range change unit 14 are executed by causing the CPU to execute processing according to a predetermined program stored in the ROM or HDD using the RAM.
- the respective functions of the control signal transmission unit 15 can be embodied in the charge and discharge control device 100.
- the degradation state determination unit 13 first uses the discharge capacity of the battery 10 based on the voltage, current, and charge / discharge time of the battery 10 represented by the battery information from the battery information acquisition unit 12.
- Q that is, the total value of the amount of electricity released from the battery 10 at the time of discharge is calculated at predetermined time intervals.
- the discharge capacity Q can be calculated by integrating the measured values of the current obtained when the battery 10 is discharging at predetermined time intervals.
- the deterioration state determination unit 13 next calculates dV / dQ indicating the ratio between the change amount dQ of the discharge capacity Q and the change amount dV of the battery voltage V at predetermined time intervals. Specifically, from the calculation results of discharge capacity Q obtained at predetermined time intervals and the measured values of the voltage and current at this time, change amount dQ of discharge capacity Q at every predetermined time interval and change amount of battery voltage V dV can be calculated, and dV / dQ can be calculated based on these calculation results.
- the deterioration state determination unit 13 determines Q indicating the relationship between the discharge capacity Q and dV / dQ based on the calculation results. Calculate the dV / dQ curve. Specifically, the horizontal axis represents the value of discharge capacity Q, and the vertical axis represents the value of dV / dQ, and these values calculated for each predetermined time are graphed to calculate the Q-dV / dQ curve. can do.
- FIG. 2 is a diagram showing an example of a discharge curve showing the relationship between the discharge capacity Q calculated by the deterioration state determination unit 13 and the measurement result of the battery voltage V corresponding to this.
- This discharge curve shows how the battery voltage V changes when the battery 10 is discharged from the fully charged state (discharge capacity 0) to the completely discharged state (maximum discharge capacity Qmax) where further discharge is impossible. It shows. From FIG. 2, it can be seen that as the discharge of the battery 10 progresses and the discharge capacity Q increases, the battery voltage V decreases.
- FIG. 3 is a diagram showing an example of the Q-dV / dQ curve calculated by the deterioration state determination unit 13.
- the Q-dV / dQ curve shows an example of the relationship between the discharge capacity Q and dV / dQ when the battery 10 is discharged from the fully charged state (discharge capacity 0) to the completely discharged state (maximum discharge capacity Qmax). There is.
- singular points B, C and D indicate that the negative electrode material graphite contributes to the discharge reaction at the negative electrode
- singular point A indicates that the negative electrode active material SiO is the negative electrode discharge It shows that it contributes to the reaction. That is, lithium ions are released from the graphite in the range where the discharge capacity Q is less than or equal to Q B , and lithium ions are released from SiO in the range where the discharge capacity Q is greater than Q B.
- the deterioration state determination unit 13 determines the deterioration state of the battery 10 as follows based on this.
- FIG. 4 is a diagram showing an example of a Q-dV / dQ curve calculated before deterioration of the battery 10 and a cycle test range.
- SOC charge state
- FIG. 4 when the charge state (SOC) of the battery 10 is in the range of 25% to 75% as a cycle test range, the charge and discharge of the battery 10 are continuously repeated within this range before the battery 10 is degraded.
- the example of the Q-dV / dQ curve calculated in the state of is shown.
- the singular points A 1 , B 1 , C 1 and D 1 before deterioration appearing at each position of the discharge capacities Q A1 , Q B1 , Q C1 and Q D1 are shown in the figure.
- the maximum discharge capacity Qmax1 when the SOC is 0% corresponds to the maximum discharge capacity Qmax in the fully discharged state of FIG.
- the Q-dV / dQ curve of the portion corresponding to the cycle test range in the figure is calculated in the deterioration state determination unit 13.
- FIG. 5 is a view showing a Q-dV / dQ curve calculated in a state where the battery 10 is deteriorated and a modification example of the cycle test range.
- the Q-dV / dQ curve calculated accordingly changes, and the position of each singular point gradually moves in the left direction of the figure.
- FIG. 5 may be singular point B 2 after degradation will fall within cycle test range before the change.
- singular points A 2 , B 2 , C 2 and D 2 after deterioration appearing at each position of discharge capacities Q A2 , Q B2 , Q C2 and Q D2 are the deteriorations shown in FIG. 4.
- the maximum discharge capacity Qmax2 after deterioration corresponds to the maximum discharge capacity Qmax1 before deterioration shown in FIG. 4, and these show the same value of dV / dQ.
- SiO which is a negative electrode active material, contributes to the charge and discharge reaction at the negative electrode and deterioration of SiO proceeds.
- the deterioration of the battery 10 will be accelerated.
- the deterioration state determination unit 13 determines that SiO as the negative electrode active material in the battery 10 contributes to the charge / discharge reaction at the negative electrode. It is determined that the battery 10 is in a deteriorated state. The determination result is output from the deterioration state determination unit 13 to the voltage range change unit 14. As a result, the deterioration state determination unit 13 notifies the voltage range change unit 14 that the battery 10 is in a deteriorated state and the voltage range for charging and discharging of the battery 10 needs to be changed.
- the deterioration state determination unit 13 can determine the deterioration state of the battery 10 by the method described above.
- voltage range change unit 14 When voltage range change unit 14 receives the determination result that battery 10 is in the deteriorated state from deterioration state determination unit 13, it recalculates SOC based on the Q-dV / dQ curve in FIG. 5. Specifically, as shown in FIG. 5, the relationship between the discharge capacity Q and the SOC is recalculated so that the SOC is 0% at the maximum discharge capacity Qmax2 after deterioration.
- the cycle test range can be changed by specifying a range of 25% to 75% in the SOC after change based on the result of the SOC recalculation.
- voltage range changing unit 14 determines the charge upper limit voltage and the discharge lower limit for battery 10 according to the cycle test range after the change. Calculate the voltage reset value respectively. Specifically, when the Q-dV / dQ curve in FIG. 5 is calculated, the relationship between the SOC in the battery 10 after deterioration and the battery voltage V is determined based on the battery information acquired by the battery information acquisition unit 12 . Based on this relationship, reset values of the charge upper limit voltage and the discharge lower limit voltage can be respectively calculated by determining the battery voltage V when the SOC is 75% and 25%.
- the voltage range changing unit 14 can change the voltage range for charging and discharging of the battery 10 by the method described above. Further, for example, the relationship between the discharge capacity of each of the positive electrode and the negative electrode and the voltage and the Q-dV / dQ curve are determined by a method as disclosed in, for example, Japanese Patent Application Laid-Open No. 2009-80093. The deterioration state of the battery 10 may be determined using a -dV / dQ curve.
- FIG. 6 is a flowchart of the charge / discharge control process executed by the charge / discharge control device 100.
- step S101 the charge / discharge control device 100 causes the battery information acquisition unit 12 to acquire battery information on the charge / discharge state of the battery 10.
- the voltage between terminals of the battery 10, the current, the charge / discharge time, and the like are acquired as battery information.
- the battery information acquisition unit 12 transmits the acquired battery information to the deterioration state determination unit 13.
- step S102 the charge / discharge control device 100 causes the deterioration state determination unit 13 to calculate the deterioration state of the battery 10 based on the battery information acquired in step S101.
- the deterioration state of the battery 10 is calculated by calculating the Q-dV / dQ curve from the battery information by the method as described above.
- step S103 the charge / discharge control device 100 causes the deterioration state determination unit 13 to determine whether the battery 10 is in the deterioration state based on the Q-dV / dQ curve obtained by the calculation of the deterioration state in step S102. judge.
- the negative electrode active material SiO contributes to the charge / discharge reaction at the negative electrode within the charge / discharge range of the battery 10 in the Q-dV / dQ curve. It is determined whether the battery 10 is in a deteriorated state by determining whether a singular point (singular point B 2 in FIG. 5) is detected.
- step S104 when it is determined that the battery is in the deteriorated state, the determination result is transmitted from the deteriorated state determining unit 13 to the voltage range changing unit 14 to warn the change of the voltage range, and the process proceeds to step S104.
- the process returns to step S101. In this case, after waiting for a predetermined time, the processes of steps S101 to S103 are performed again.
- the conditions for determining that the battery 10 is in the deteriorated state in step S103 may be conditions other than the above.
- an intermediate point of discharge capacities Q A2 and Q B2 corresponding to singular points A 2 and B 2 respectively is taken, and this intermediate point is within the charge / discharge range of battery 10
- it reaches it is determined that the battery 10 is in a deteriorated state.
- the deterioration of the negative electrode active material SiO did not progress so much, and the deterioration of the battery 10 could be suppressed.
- step S104 the charge / discharge control device 100 causes the voltage range change unit 14 to recalculate the SOC based on the determination result of the deterioration state in step S103.
- the relationship between the discharge capacity Q and the SOC is recalculated according to the deterioration state of the battery 10 using the Q-dV / dQ curve obtained in step S102.
- step S105 the charge / discharge control device 100 causes the voltage range change unit 14 to change the charge upper limit voltage and the discharge lower limit voltage for the battery 10 based on the result of the SOC recalculation in step S104.
- the range of the charge / discharge voltage of the battery 10 is reset according to the relationship between the discharge capacity Q and the SOC recalculated in step S104, and the reset values of the charge upper limit voltage and the discharge lower limit voltage are adjusted according to the range. calculate. At this time, only one of the charge upper limit voltage and the discharge lower limit voltage may be changed.
- the voltage range change unit 14 transmits the calculated reset values to the control signal transmission unit 15. Thereby, the control signal transmitting unit 15 transmits a control signal according to the changed charge upper limit voltage and discharge lower limit voltage to the controller 11, and the range of the charge and discharge voltage of the battery 10 is changed.
- step S105 the charge / discharge control device 100 ends the charge / discharge control process of FIG. Then, after waiting for a predetermined time, the charge / discharge control process of FIG. 6 is executed again from step S101.
- the voltage range change unit 14 receives the warning output from the deterioration state determination unit 13 in step S103, the user is allowed to select whether to change the range of the charge and discharge voltage of the battery 10 or not. It is also good. In this case, when the user selects the change of the charge / discharge voltage range, the voltage range change unit 14 executes the processes of steps S104 and S105. On the other hand, when the user does not select to change the range of the charge / discharge voltage, the charge / discharge control process of FIG. 6 ends as it is without executing the process of steps S104 and S105 in the voltage range change unit.
- Lithium ion batteries are usually used in a SOC range of about 25% to 75%.
- SOC is a value defined by the user and can not be measured. Therefore, in the energization control of the battery 10 by the controller 11, the upper limit value and the lower limit value of the battery voltage V during charging / discharging are within the SOC range in which the battery 10 is used, for example, 25%
- the charge and discharge of the battery 10 are controlled to have a value corresponding to the 75% SOC range.
- the life of the battery 10 may be shortened.
- the charge and discharge capacity of the battery 10 may not be sufficiently utilized.
- the charge upper limit voltage and the discharge lower limit voltage are changed by the charge / discharge control device 100 according to the deterioration state of the battery 10. This point will be specifically described below with reference to FIG.
- FIG. 7 is a view showing an example of a charge / discharge curve corresponding to the battery 10 in the initial state and a charge / discharge curve corresponding to the battery 10 in the deteriorated state.
- the charge upper limit voltage is changed by the charge / discharge control device 100 according to the deterioration state of the battery 10. That is, when the battery 10 is deteriorated, the charging upper limit voltage is changed from V1 to V2 accordingly. At this time, the charging upper limit voltage does not necessarily have to be V2, and the charging upper limit voltage may be changed so as to approach V2. In this way, even if the battery 10 is degraded, charging can not be completed when the SOC is 55%, and charging can be performed until the SOC becomes about 70% as in the initial state. Therefore, even if the battery 10 is degraded, the decrease in capacity of the usable battery 10 can be avoided.
- the change of the charge upper limit voltage is described, but the same can be said of the change of the discharge lower limit voltage. That is, by changing the discharge lower limit voltage in accordance with the deterioration state of the battery 10, it is possible to avoid a decrease in capacity of the usable battery 10 even if the battery 10 is deteriorated.
- FIG. 8 is a view showing a configuration example of the electrode assembly 4 constituting the battery 10.
- FIG. 9 is a view showing how the electrode assembly 4 is sandwiched between the sheets 7.
- FIG. 10 is a view showing how the sheet 7 is thermally welded.
- the electrode body 4 has a positive electrode 1, a negative electrode 2 and a bag-like separator 3.
- the positive electrode 1 is connected to the positive electrode terminal 5, and the negative electrode 2 is connected to the negative electrode terminal 6.
- the weight of layered LiMO 2 (M represents Ni 0.5 Co 0.2 Mn 0.3) as a positive electrode active material, acetylene black as a conductive material, and polyvinylidene fluoride (PVdF) as a binder What mixed N- methyl pyrrolidone (NMP) as a solvent so that it might become 93: 4: 3 in ratio was used as a positive electrode mixture slurry.
- the positive electrode mixture slurry was applied to a 15 ⁇ m thick aluminum foil, dried in the air, and then formed into a size of 45 mm ⁇ 70 mm by a roll press, and cut into a shape to which a current collector foil exposed portion was added. .
- the positive electrode 1 was produced.
- the solvent of water is used so that the weight ratio of graphite, SiO, carboxymethylcellulose (CMC) as a binder, and styrene butadiene rubber (SBR) is 93: 5: 1: 1.
- the mixture was used as a negative electrode mixture slurry.
- the negative electrode mixture slurry was applied to a copper foil having a thickness of 10 ⁇ m and dried in the air, and then formed into a size of 45 mm ⁇ 70 mm by a roll press, and cut into a shape to which a current collector foil exposed portion was added. .
- a negative electrode 2 was produced.
- separator 3 a film material with a total thickness of 0.03 mm in which polypropylene, polyethylene, and polypropylene were laminated in three layers was used. Two pieces of this film material were used to sandwich the positive electrode 1 and the three sides around the periphery were heat-welded to form a bag, whereby a separator 3 was produced.
- the positive electrode 1 and the negative electrode 2 are inserted into the bag-like separator 3, and the positive electrode terminal 5 and the negative electrode terminal 6 are connected by ultrasonic welding in a state where the exposed portions of the current collector foils are exposed to the outside of the separator 3 Thus, an electrode assembly 4 as shown in FIG. 8 was produced.
- the electrode assembly 4 was disposed between the two heat weldable sheets 7, and the electrode assembly 4 was sandwiched between the sheets 7.
- two sheets 7 were heat-welded in the heat-welding portion 8 except for the injection port (not shown) for injecting the electrolyte.
- the injection port was sealed by heat welding.
- an electrolyte impregnation time of 8 hours was provided. Thereafter, the battery 10 was completed by charging and discharging for 3 cycles with a current value of 0.2 CA within a voltage range of 4.2 V to 2.5 V.
- FIG. 11 is a table showing the results of this cycle test.
- the cycle test result in the case where the voltage range of charge and discharge is performed twice according to the deterioration state of the battery 10 during the cycle test is shown as Example 1, and the cycle test result in the case where it is performed once is an example. It is shown as 2.
- the cycle test result in case the voltage range of charging / discharging was not performed even once is shown as the comparative example 1.
- FIG. 12 is a table showing details of the cycle test results of Example 1.
- SOC is recalculated and the voltage of charge and discharge is calculated. The range has changed.
- SiO which is a negative electrode active material, contributes to the charge / discharge reaction at the negative electrode, thereby suppressing the progress of the deterioration of the battery 10 and reducing the capacity retention ratio of the battery 10 to about 80%. It was possible to carry out charge and discharge cycles.
- FIG. 13 is a table showing the details of the cycle test results of Example 2.
- SOC is recalculated and the voltage range of charge and discharge is changed. It was done.
- SiO which is a negative electrode active material, contributes to the charge / discharge reaction at the negative electrode, thereby suppressing the progress of the deterioration of the battery 10 and reducing the capacity retention ratio of the battery 10 to about 80%. It was possible to carry out charge and discharge cycles.
- FIG. 14 is a table showing details of the cycle test results of Comparative Example 1. As shown in FIG. 14, in Comparative Example 1, charge and discharge of the battery 10 were continued without changing the charge and discharge voltage range. As a result, the number of charge and discharge cycles until the capacity retention rate of the battery 10 decreased to about 80% was 4,000 times, which is smaller than in the above-described Examples 1 and 2.
- the charge and discharge control device 100 controls the charge and discharge of the battery 10 having SiO, which is a negative electrode active material.
- the charge / discharge control device 100 determines the deterioration state of the battery 10 based on the battery information acquisition unit 12 that acquires battery information on the charge / discharge state of the battery 10 and the battery information acquired by the battery information acquisition unit 12.
- a deterioration state determination unit 13 and a voltage range change unit 14 that changes the voltage range for charging and discharging of the battery 10 based on the determination result of the deterioration state by the deterioration state determination unit 13 are provided. As a result, the cycle characteristics of the battery 10 can be effectively improved.
- the deterioration state determination unit 13 determines the ratio of the change amount dV of the battery voltage V to the discharge capacity Q of the battery 10 and the change amount dQ of the discharge capacity Q based on the battery information acquired by the battery information acquisition unit 12 A Q-dV / dQ curve indicating a relationship with dV / dQ shown is calculated (step S102), and the deterioration state of the battery 10 is determined based on the Q-dV / dQ curve (step S103). Since it did in this way, the degradation state of the battery 10 can be determined correctly.
- the voltage range change unit 14 recalculates SOC for recalculating the relationship between the discharge capacity Q of the battery 10 and the state of charge SOC of the battery 10 based on the determination result of the deterioration state by the degradation state determination unit 13 (Step S104), and the voltage range for charging and discharging of the battery 10 is changed based on the result of the SOC recalculation (step S105). Since it did in this way, according to the deterioration state of the battery 10, the voltage range with respect to charging / discharging of the battery 10 can be changed suitably.
- the Q-dV / dQ curve is calculated based on the acquired battery information, and in the Q-dV / dQ curve, whether a specific singular point is within the charge / discharge range of the battery 10
- the deterioration state of the battery 10 may be determined by another method. For example, the positional relationship of each singular point in the Q-dV / dQ curve can be determined, and the deterioration state of the battery 10 can be determined from this positional relationship.
- the deterioration state of the battery 10 can be determined by various methods in accordance with the type of the active material used in the battery 10, the electrode material, and the like.
- the configuration of the lithium ion battery to be controlled in the charge and discharge control method and the charge and discharge control device of the present invention is not limited to that described in the above embodiment.
- the specific configuration is not particularly limited as long as it contains a positive electrode capable of absorbing and desorbing lithium ions, a negative electrode capable of absorbing and desorbing lithium ions, and a lithium salt.
- a battery using a non-aqueous electrolyte may be used, or a battery containing a lithium ion polymer may be used.
- the battery may be a battery containing a solid electrolyte, or a battery containing an ionic liquid.
- the separator is not an essential component, and may be used as needed.
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Abstract
Description
本発明による充放電制御装置は、負極活物質を有するリチウムイオン電池の充放電を制御するものであって、リチウムイオン電池の充放電状態に関する電池情報を取得する電池情報取得部と、電池情報取得部により取得された電池情報に基づいて、リチウムイオン電池の劣化状態を判定する劣化状態判定部と、劣化状態判定部による劣化状態の判定結果に基づいて、リチウムイオン電池の充放電に対する電圧範囲を変更する電圧範囲変更部と、を備える。
図1は、本発明の一実施形態による充放電制御装置100の構成を示すブロック図である。図1に示した充放電制御装置100は、二次電池であるリチウムイオン電池10(以下、単に電池10と称する)の充放電を制御するための装置であり、電池情報取得部12と、劣化状態判定部13と、電圧範囲変更部14と、制御信号送信部15とを機能的に有する。充放電制御装置100は、電池10およびコントローラ11に接続されている。
次に、劣化状態判定部13による電池10の劣化状態の判定方法および電圧範囲変更部14による電池10の充放電に対する電圧範囲の変更方法について説明する。
次に、電池10の充放電制御を行う際に充放電制御装置100により実行される充放電制御処理について説明する。図6は、充放電制御装置100により実行される充放電制御処理のフローチャートである。
次に、電池10の構成について、図8~10を参照して説明する。以下では、ロッキングチェア型のリチウムイオン二次電池を用いた電池10の構成例について説明する。図8は、電池10を構成する電極体4の構成例を示す図である。図9は、電極体4をシート7の間に挟み込む様子を示す図である。図10は、シート7を熱溶着した様子を示す図である。
次に、以上説明したようにして作製された電池10を用いて、図1に示したような構成により、電池10のサイクル試験を行った結果について説明する。なお、サイクル試験の実施に当たっては、劣化前の電池10の特性データとして、初期状態での電池容量および内部抵抗の値を事前に測定すると共に、0.02CAで電池10を充放電させたときの充放電カーブを取得した。
2 負極
3 セパレータ
4 電極体
5 正極端子
6 負極端子
7 シート
8 熱溶着部
10 リチウムイオン電池
11 コントローラ
12 電池情報取得部
13 劣化状態判定部
14 電圧範囲変更部
15 制御信号送信部
100 充放電制御装置
Claims (6)
- 負極活物質を有するリチウムイオン電池の充放電制御方法であって、
前記リチウムイオン電池は、充放電制御装置に接続されており、
前記充放電制御装置により、前記リチウムイオン電池の充放電状態に関する電池情報を取得し、
前記充放電制御装置により、前記電池情報に基づいて、前記リチウムイオン電池の劣化状態を判定し、
前記充放電制御装置により、前記劣化状態の判定結果に基づいて、前記リチウムイオン電池の充放電に対する電圧範囲を変更する、リチウムイオン電池の充放電制御方法。 - 請求項1に記載のリチウムイオン電池の充放電制御方法において、
前記充放電制御装置により、前記電池情報に基づいて、前記リチウムイオン電池の放電容量Qと前記放電容量Qの変化量dQに対する電池電圧Vの変化量dVの割合を示すdV/dQとの関係を示すQ-dV/dQ曲線を算出し、前記Q-dV/dQ曲線に基づいて前記リチウムイオン電池の劣化状態を判定する、リチウムイオン電池の充放電制御方法。 - 請求項1または2に記載のリチウムイオン電池の充放電制御方法において、
前記充放電制御装置により、前記劣化状態の判定結果に基づいて、前記リチウムイオン電池の放電容量Qと前記リチウムイオン電池の充電状態SOCとの関係を再計算するためのSOC再計算を行い、前記SOC再計算の結果に基づいて前記電圧範囲を変更する、リチウムイオン電池の充放電制御方法。 - 負極活物質を有するリチウムイオン電池の充放電を制御する充放電制御装置であって、
前記リチウムイオン電池の充放電状態に関する電池情報を取得する電池情報取得部と、
前記電池情報取得部により取得された前記電池情報に基づいて、前記リチウムイオン電池の劣化状態を判定する劣化状態判定部と、
前記劣化状態判定部による前記劣化状態の判定結果に基づいて、前記リチウムイオン電池の充放電に対する電圧範囲を変更する電圧範囲変更部と、を備える充放電制御装置。 - 請求項4に記載の充放電制御装置において、
前記劣化状態判定部は、前記電池情報に基づいて、前記リチウムイオン電池の放電容量Qと前記放電容量Qの変化量dQに対する電池電圧Vの変化量dVの割合を示すdV/dQとの関係を示すQ-dV/dQ曲線を算出し、前記Q-dV/dQ曲線に基づいて前記リチウムイオン電池の劣化状態を判定する、充放電制御装置。 - 請求項4または5に記載の充放電制御装置において、
前記電圧範囲変更部は、前記劣化状態の判定結果に基づいて、前記リチウムイオン電池の放電容量Qと前記リチウムイオン電池の充電状態SOCとの関係を再計算するためのSOC再計算を行い、前記SOC再計算の結果に基づいて前記電圧範囲を変更する、充放電制御装置。
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