WO2009090913A1 - リチウムイオン二次電池の充電方法、及び、ハイブリッド自動車 - Google Patents
リチウムイオン二次電池の充電方法、及び、ハイブリッド自動車 Download PDFInfo
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- WO2009090913A1 WO2009090913A1 PCT/JP2009/050208 JP2009050208W WO2009090913A1 WO 2009090913 A1 WO2009090913 A1 WO 2009090913A1 JP 2009050208 W JP2009050208 W JP 2009050208W WO 2009090913 A1 WO2009090913 A1 WO 2009090913A1
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- charging
- lithium ion
- ion secondary
- secondary battery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L53/00—Methods of charging batteries, specially adapted for electric vehicles; Charging stations or on-board charging equipment therefor; Exchange of energy storage elements in electric vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W10/00—Conjoint control of vehicle sub-units of different type or different function
- B60W10/04—Conjoint control of vehicle sub-units of different type or different function including control of propulsion units
- B60W10/06—Conjoint control of vehicle sub-units of different type or different function including control of propulsion units including control of combustion engines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W10/00—Conjoint control of vehicle sub-units of different type or different function
- B60W10/24—Conjoint control of vehicle sub-units of different type or different function including control of energy storage means
- B60W10/26—Conjoint control of vehicle sub-units of different type or different function including control of energy storage means for electrical energy, e.g. batteries or capacitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W20/00—Control systems specially adapted for hybrid vehicles
- B60W20/10—Controlling the power contribution of each of the prime movers to meet required power demand
- B60W20/13—Controlling the power contribution of each of the prime movers to meet required power demand in order to stay within battery power input or output limits; in order to prevent overcharging or battery depletion
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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
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/007—Regulation of charging or discharging current or voltage
- H02J7/0071—Regulation of charging or discharging current or voltage with a programmable schedule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W20/00—Control systems specially adapted for hybrid vehicles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W2510/00—Input parameters relating to a particular sub-units
- B60W2510/24—Energy storage means
- B60W2510/242—Energy storage means for electrical energy
- B60W2510/244—Charge state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60W—CONJOINT CONTROL OF VEHICLE SUB-UNITS OF DIFFERENT TYPE OR DIFFERENT FUNCTION; CONTROL SYSTEMS SPECIALLY ADAPTED FOR HYBRID VEHICLES; ROAD VEHICLE DRIVE CONTROL SYSTEMS FOR PURPOSES NOT RELATED TO THE CONTROL OF A PARTICULAR SUB-UNIT
- B60W2520/00—Input parameters relating to overall vehicle dynamics
- B60W2520/10—Longitudinal speed
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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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- 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
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/7072—Electromobility specific charging systems or methods for batteries, ultracapacitors, supercapacitors or double-layer capacitors
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/10—Technologies relating to charging of electric vehicles
- Y02T90/14—Plug-in electric vehicles
Definitions
- the present invention relates to a method for charging a lithium ion secondary battery and a hybrid vehicle.
- Lithium ion secondary batteries are attracting attention as a power source for portable devices and as a power source for electric vehicles and hybrid vehicles. At present, various methods for charging the lithium ion secondary battery have been proposed (see, for example, Patent Documents 1 to 3).
- Patent Document 1 discloses a charging method using a pulse current method in which energization and stop are repeated. Specifically, the lithium ion secondary battery is charged by repeating energization for 0.1 to 10 milliseconds and stopping for 0.5 to 100 milliseconds. This describes that dendrite growth can be prevented and charging can be repeated many times without causing poor charging.
- Patent Document 2 discloses a charging method in which charging is performed at a constant current until the battery voltage reaches a full charge voltage, and intermittent charge is performed by repeating charge stop and constant current charge after reaching the full charge voltage. Thus, it is described that battery destruction due to overcharging can be prevented and charging to full charge capacity can be performed without excess or deficiency.
- Patent Document 3 discloses an intermittent charging method in which energization and pause are repeated. Specifically, the charging rate is set to 20 C, and charging for 10 seconds and pause for 0.8 seconds are repeated to charge the lithium ion secondary battery. This describes that the effective capacity of the battery can be increased.
- the hybrid vehicle when the storage amount of the lithium ion secondary battery mounted as the driving power source is reduced to the first specified value (for example, the storage amount corresponding to SOC 30%), the hybrid vehicle is stopped during traveling.
- the lithium ion secondary battery may be charged until the charged amount of the lithium ion secondary battery reaches a second specified value (for example, the charged amount corresponding to SOC 60%).
- metal Li may be deposited on the negative electrode surface. This is presumably because Li ions that were not taken into the negative electrode were deposited on the negative electrode surface as metallic Li due to the diffusion-controlled Li ions. For this reason, when such charging is repeated, a large amount of metal Li may be deposited on the negative electrode surface. The metal Li once deposited on the negative electrode surface is difficult to contribute to charge transfer again as Li ions, and as a result, there is a possibility that the battery is greatly deteriorated (electric capacity is greatly reduced).
- the charging method of Patent Document 2 is a method of continuously charging with a constant current until the battery voltage reaches a fully charged voltage. For this reason, when the charging method of Patent Document 2 is applied to the charging of the lithium ion secondary battery while the hybrid vehicle is stopped, the metal Li is deposited on the surface of the negative electrode every time charging is performed. It is considered that the battery deteriorates (electric capacity greatly decreases) at an early stage.
- Patent Document 1 or Patent Document 3 if charging and pause for a short time are repeated, idling of the hybrid vehicle becomes unstable. Thereby, riding comfort may be impaired and a driver
- the present invention has been made in view of the present situation, it is possible to suppress the precipitation of metal Li on the negative electrode surface, it is possible to suppress the decrease in electric capacity, and does not impair riding comfort, It is an object of the present invention to provide a method for charging a lithium ion secondary battery mounted on a hybrid vehicle and a hybrid vehicle.
- the solution is a method for charging a lithium ion secondary battery mounted on a hybrid vehicle as a power source for driving, wherein the value of the physical quantity corresponding to the charged amount of the lithium ion secondary battery reaches the first specified value.
- a step of determining whether or not the vehicle is in a stopped state, a step of determining whether or not the hybrid vehicle is in a travel stop state, and a value of a physical quantity corresponding to a storage amount of the lithium ion secondary battery is the first specified value.
- the present invention relates to a method for charging a lithium ion secondary battery mounted on a hybrid vehicle as a driving power source, wherein the physical quantity value corresponding to the charged amount of the lithium ion secondary battery is reduced to a first specified value.
- the present invention relates to a method of charging the lithium ion secondary battery until the value of the physical quantity corresponding to the storage amount of the lithium ion secondary battery reaches a second specified value.
- the period for charging until the value of the physical quantity corresponding to the amount of stored electricity that has decreased to the first specified value reaches the second specified value is divided into two or more divided charging periods and each divided charging period.
- the battery is divided into a non-charging period, and charging is performed during the divided charging period, and at least one of charging suspension and discharging is performed during the non-charging period.
- the length of each divided charging period is 40 seconds or more.
- the “physical quantity corresponding to the charged amount” refers to a physical quantity that corresponds to the charged amount on a one-to-one basis in addition to the charged amount, and includes, for example, SOC and battery voltage (terminal voltage).
- examples of the first specified value include a storage amount corresponding to SOC 30%, a voltage value between terminals of the battery in this storage state, and the like.
- examples of the second specified value include a storage amount corresponding to SOC 60%, a voltage value between terminals of the battery in this storage state, and the like.
- “perform at least one of charging suspension and discharging during the non-charging period” means that charging may be suspended throughout the non-charging period, or discharging may be performed throughout the non-charging period. Also good. Further, a non-charging period in which charging is suspended and a non-charging period in which discharging is performed may be mixed. Further, pause and discharge may be performed within one non-charging period.
- the non-charging period is a charging suspension period in which charging of the lithium ion secondary battery is suspended, and the length tc of each of the divided charging periods;
- the non-charging period is the charging suspension period. That is, charging is suspended over the entire non-charging period. Therefore, split charging is performed with a pause in between until the value of the physical quantity corresponding to the charged amount reaches the second specified value.
- the charging suspension period is too short with respect to the divided charging period, Li ions staying at the interface between the electrolytic solution and the negative electrode cannot be sufficiently diffused due to diffusion control, and the deposition of metallic Li on the negative electrode surface Cannot be sufficiently suppressed.
- the ratio tr / tc between the length tc of each divided charging period and the length tr of the charging suspension period immediately after that is 0.14 or more. Thereby, it can suppress that metal Li precipitates on the negative electrode surface.
- the charging suspension period is lengthened, the deposition of metal Li on the negative electrode surface can be suppressed.
- the charging suspension period is excessively long, it corresponds to the charged amount of the lithium ion secondary battery during the travel stop. There is a possibility that the value of the physical quantity cannot be recovered to the second specified value.
- the charging suspension period is sufficient to allow diffusion of Li ions staying at the interface between the electrolyte and the negative electrode due to diffusion control, and further charging suspension is wasted.
- tr / tc is set to 0.9 or less. Thereby, the value of the physical quantity corresponding to the storage amount of the lithium ion secondary battery can be promptly and appropriately recovered to the second specified value without spending useless charging suspension time.
- the said non-charging period is made into the discharge period which discharges the said lithium ion secondary battery.
- the non-charging period is set as the discharging period. That is, discharging is performed over the entire non-charging period. Therefore, the divided charge is performed with the discharge interposed therebetween until the value of the physical quantity corresponding to the charged amount reaches the second specified value. Thereby, the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value can be charged quickly until it reaches the second specified value.
- each of the non-charge periods includes a charge suspension period in which charging of the lithium ion secondary battery is paused and a discharge in which the lithium ion secondary battery is discharged. It is preferable to use a charging method for a lithium ion secondary battery.
- each non-charging period is a charging suspension period and a discharging period. That is, charging is stopped and discharged in each non-charging period. Therefore, split charging is performed with charging pause and discharging in between until the value of the physical quantity corresponding to the charged amount reaches the second specified value. Thereby, the fall of an electrical capacitance can be suppressed further.
- the charging method of the present invention it is determined whether or not the engine mounted on the hybrid vehicle is in an operating state, and when it is determined that the engine is not operating, the operation of the engine is instructed. Thereby, the electric power generated by this generator can be supplied to the lithium ion secondary battery while the generator mounted on the hybrid vehicle is driven by the operation of the engine. Therefore, the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value can be appropriately charged until it reaches the second specified value.
- the charging step may be a method for charging a lithium ion secondary battery in which the lithium ion secondary battery is charged with a current of 2C or more.
- the lithium ion secondary battery is charged with a current of 2 C or more.
- the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value is charged in a shorter time until it reaches the second specified value. Can do.
- the charging time can be shortened as described above, but on the other hand, Li ions are easily retained at the interface between the electrolytic solution and the negative electrode due to the diffusion rate limiting of Li ions. .
- the charging method of the present invention as described above, during charging to the first specified value or the second specified value, at least one of rest and discharge is performed, so that it stays at the interface between the electrolyte and the negative electrode. It is possible to suppress the deposition of metal Li on the negative electrode surface by diffusing Li ions that are present.
- the charging current is increased, it is preferable in that the charging can be performed in a shorter time until the second specified value is reached.
- the magnitude of the charging current is preferably 2C or more and 10C or less, for example.
- a hybrid vehicle in which a lithium ion secondary battery mounted on the hybrid vehicle as a driving power source and a physical quantity value corresponding to a storage amount of the lithium ion secondary battery are defined as a first regulation.
- a stop state determination means for determining whether or not the hybrid vehicle is in a travel stop state, and a storage amount of the lithium ion secondary battery
- the lithium ion is Charge control means for performing charge control of the lithium ion secondary battery until the value of the physical quantity corresponding to the charged amount of the secondary battery reaches a second specified value,
- the charging period is divided into two or more divided charging periods and a non-charging period between each of the divided charging periods, charging is performed during the divided charging period, and charging is suspended during the non-charging period.
- a charge control unit that performs at least one
- the lithium ion secondary Charge control means is provided for performing charge control of the lithium ion secondary battery until the value of the physical quantity corresponding to the storage amount of the secondary battery reaches the second specified value.
- the charging control means includes two or more divided charging periods and a period during which charging is performed until the value of the physical quantity corresponding to the storage amount that has decreased to the first specified value reaches the second specified value.
- the battery is divided into a non-charging period, and charging is performed during the divided charging period, and at least one of charging suspension and discharging is performed during the non-charging period.
- the charging control means sets the length of each divided charging period to 40 seconds or more.
- the idling of the hybrid vehicle can be stabilized by lengthening the one split charging period, the riding comfort is not impaired.
- the charge control unit sets the non-charging period as a charging suspension period in which charging of the lithium ion secondary battery is suspended, and a length tc of each of the divided charging periods;
- the ratio tr / tc with respect to the length tr of the charging suspension period immediately after that may be set to 0.14 or more and 0.9 or less to be a hybrid vehicle that performs charging control of the lithium ion secondary battery.
- the charging control means sets the non-charging period as the charging suspension period. That is, charging is suspended over the entire non-charging period. Therefore, split charging is performed with a pause in between until the value of the physical quantity corresponding to the charged amount reaches the second specified value.
- the ratio tr / tc between the length tc of each divided charging period and the length tr of the charging suspension period immediately after that is 0.14 or more and 0.9 or less.
- the said charge control means is good to make the said non-charging period into a hybrid vehicle which becomes a discharge period which discharges the said lithium ion secondary battery.
- the non-charging period is set to the discharging period in the charging control means. That is, the lithium ion secondary battery is discharged over the entire non-charging period. Therefore, split charging is performed with the discharge in between until the value of the physical quantity corresponding to the charged amount of the lithium ion secondary battery reaches the second specified value. Thereby, the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value can be charged quickly until it reaches the second specified value.
- the charge control unit is configured to discharge each of the non-charging periods, a charging suspension period in which charging of the lithium ion secondary battery is suspended and discharging the lithium ion secondary battery. It is better to make it a hybrid car with a period.
- each non-charging period is set to a charging suspension period and a discharging period. That is, charging is stopped and discharged in each non-charging period. Therefore, split charging is performed with charging pause and discharging in between until the value of the physical quantity corresponding to the charged amount of the lithium ion secondary battery reaches the second specified value. Thereby, the fall of an electrical capacitance can be suppressed further.
- any of the above hybrid vehicles when it is determined that the engine operation determining means for determining whether the engine mounted on the hybrid vehicle is operating, and the engine is not operating, Engine operation instruction means for instructing the operation of the engine, and the charge control means generates power by the generator while the generator mounted on the hybrid vehicle is driven by the operation of the engine. It is preferable to use a hybrid vehicle that performs control for supplying the generated power to the lithium ion secondary battery and charging the lithium ion secondary battery.
- the hybrid vehicle of the present invention it is determined whether or not the mounted engine is in an operating state, and if it is determined that the engine is not operating, the operation of the engine is instructed. Thereby, the electric power generated by this generator can be supplied to the lithium ion secondary battery while the generator mounted on the hybrid vehicle is driven by the operation of the engine. Therefore, the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value can be appropriately charged until it reaches the second specified value.
- the charge control means may be a hybrid vehicle that performs control for charging the lithium ion secondary battery with a current of 2 C or more.
- the lithium ion secondary battery is charged with a current of 2C or more.
- the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value is charged in a shorter time until it reaches the second specified value.
- the lithium ion secondary battery in which the value of the physical quantity corresponding to the charged amount is reduced to the first specified value is charged in a shorter time until it reaches the second specified value.
- at least one of rest and discharge is performed, so that Li ions staying at the interface between the electrolyte and the negative electrode are diffused.
- the deposition of metal Li on the negative electrode surface can be suppressed.
- the charging period until the second specified value can be shortened.
- the magnitude of the charging current is preferably 2C or more and 10C or less, for example.
- FIG. 1 is a schematic diagram of a hybrid vehicle according to Examples 1 to 17.
- FIG. 1 is a schematic diagram of a battery system according to Examples 1 to 17.
- FIG. It is explanatory drawing explaining the charging method concerning Example 1.
- FIG. It is sectional drawing of a lithium ion secondary battery. It is sectional drawing of an electrode body. It is a partial expanded sectional view of an electrode body, and is equivalent to the B section enlarged view of FIG. 3 is a flowchart showing a flow of a charging method for a lithium ion secondary battery according to Example 1; 6 is a graph showing cycle test results according to Examples 1 and 2 and Comparative Example 1; 6 is a graph showing cycle test results according to Examples 3 to 5 and Comparative Example 2.
- a hybrid vehicle 1 includes a vehicle body 2, an engine 3, a front motor 4, a rear motor 5, a battery system 6, a cable 7, and a generator 9, as shown in FIG.
- This is a hybrid vehicle that is driven in combination with the motor 4 and the rear motor 5.
- the hybrid vehicle 1 is configured to be able to travel using the engine 3, the front motor 4, and the rear motor 5 by known means using the battery system 6 as a driving power source for the front motor 4 and the rear motor 5.
- the battery system 6 as a driving power source for the front motor 4 and the rear motor 5.
- the battery system 6 is attached to the vehicle body 2 of the hybrid vehicle 1 and is connected to the front motor 4 and the rear motor 5 by a cable 7.
- the battery system 6 includes a battery pack 10 in which a plurality of lithium ion secondary batteries 100 (single cells) are electrically connected in series with each other, a voltage detection unit 40, a current detection unit 50, and the like.
- the battery controller 30 is provided.
- the battery controller 30 includes a ROM 31, a CPU 32, a RAM 33, and the like.
- the voltage detection means 40 detects the voltage V between the terminals of each lithium ion secondary battery 100. Further, the current detection means 50 detects the current value I flowing through the lithium ion secondary battery 100 constituting the assembled battery 10.
- the battery controller 30 stores the charge of the lithium ion secondary battery 100 based on the inter-terminal voltage V (specifically, the average value of the lithium ion secondary battery 100 constituting the assembled battery 10) detected by the voltage detection means 40. The amount is calculated, and the SOC (State Of Charge) of the lithium ion secondary battery 100 is estimated from the calculated amount of stored electricity. Furthermore, the battery controller 30 determines whether or not the storage amount of the lithium ion secondary battery 100 has decreased to a first specified value (in the first embodiment, the storage amount corresponding to SOC 30%). In the first embodiment, it is determined whether or not the estimated SOC has decreased to 30%.
- the battery controller 30 determines whether or not the hybrid vehicle 1 is in a stopped state. Specifically, based on a signal transmitted from ECU 60, it is determined whether hybrid vehicle 1 is in a stopped state. When the battery system 6 is in the activated state and the shift position is the “N position” or the “P position”, the ECU 60 determines that the hybrid vehicle 1 is in the stopped state and outputs a stop state signal indicating that it is in the stopped state. It transmits to the battery controller 30. Further, even when the shift position is “D position”, the accelerator is not depressed, and the vehicle speed is “0”, it is determined that the hybrid vehicle 1 is in a stopped state, and a stop state signal is sent to the battery controller 30. Send. When the battery controller 30 detects the stop state signal, the battery controller 30 determines that the hybrid vehicle 1 is in the stop state.
- the battery controller 30 determines whether or not the engine 3 mounted on the hybrid vehicle 1 is operating. Specifically, it is determined based on a signal transmitted from the ECU 60 whether or not the engine 3 is operating. When the engine speed is not “0”, the ECU 60 determines that the engine 3 is operating, and transmits an operating state signal indicating that the engine 3 is operating to the battery controller 30. The battery controller 30 determines that the engine 3 is operating when this operating state signal is detected.
- the battery controller 30 instructs the operation of the engine 3. As a result, the engine 3 enters an operating state (idling state), and the generator 9 (alternator) is driven accordingly.
- the battery controller 30 determines that the amount of power stored in the lithium ion secondary battery 100 has decreased to the first specified value (the estimated SOC has decreased to 30%), and the hybrid vehicle 1 is in the travel stop state.
- the lithium ion secondary battery 100 is controlled to be charged until the charged amount of the lithium ion secondary battery 100 reaches the second specified value.
- the generator 9 is driven by the operation of the engine 3
- the electric power generated by the generator 9 is supplied to the lithium ion secondary battery 100 constituting the assembled battery 10.
- the second specified value is the amount of power stored corresponding to SOC 60%. Therefore, the battery controller 30 continues to charge the lithium ion secondary battery 100 until the estimated SOC reaches 60%. In addition, since the theoretical electric capacity of the lithium ion secondary battery 100 is 5 Ah, the amount of electricity stored corresponding to SOC 100% is 5 Ah.
- the battery controller 30 corresponds to a first determination unit, a stop state determination unit, an engine operation determination unit, an engine operation instruction unit, and a charge control unit.
- the battery controller 30 divides the charging period until the charged amount of the lithium ion secondary battery 100 reaches the second specified value into two or more divided charging periods and a non-charging period between the divided charging periods. To divide. Then, charging is performed during the divided charging period, and charging is suspended during the non-charging period.
- the charging period K is divided into two divided charging periods (a first divided charging period KC1 and a second divided charging period KC2) and a non-charging period between the divided charging periods. It is divided into (charging suspension period KR), and “charging, suspension, charging” is performed to restore the stored power amount to the second specified value.
- the charging suspension period KR within the charging period K from the first specified value to the second specified value, it is possible to suppress the deposition of metal Li on the negative electrode surface. This is considered to be because Li ions staying at the interface between the electrolytic solution and the negative electrode can be diffused by diffusion-controlled in the lithium ion secondary battery 100 by stopping charging. Thereby, the fall of the electrical capacity accompanying precipitation of metal Li can be suppressed.
- the length tc of the divided charging period may be 40 seconds or more.
- the length tc of the first divided charging period KC1 is set to 67.5 seconds
- the length of the second divided charging period KC2 is set.
- the length tc is also 67.5 seconds.
- the magnitude of the charging current is preferably 2 C or more and 10 C or less, and in the first embodiment, the constant current is 8 C (40 A) in the first divided charging period KC1 and the second divided charging period KC2.
- the constant current is 8 C (40 A) in the first divided charging period KC1 and the second divided charging period KC2.
- the lithium ion secondary battery 100 is a rectangular sealed lithium ion secondary battery including a rectangular parallelepiped battery case 110, a positive electrode terminal 120, and a negative electrode terminal 130.
- the battery case 110 is made of metal, and includes a rectangular housing portion 111 that forms a rectangular parallelepiped housing space, and a metal lid portion 112.
- An electrode body 150, a positive electrode current collector member 122, a negative electrode current collector member 132, a non-aqueous electrolyte solution 140, and the like are accommodated in the battery case 110 (rectangular container 111).
- the positive electrode plate 155 is coated with a positive electrode mixture 152 including a positive electrode active material 153 at a portion excluding the positive electrode winding portion 155b (see FIG. 6).
- the negative electrode plate 156 is coated with a negative electrode mixture 159 including a negative electrode active material 154 at a portion other than the negative electrode winding portion 156b (see FIG. 6).
- the positive electrode winding part 155 b is electrically connected to the positive electrode terminal 120 through the positive electrode current collecting member 122.
- the negative electrode winding part 156 b is electrically connected to the negative electrode terminal 130 through the negative electrode current collecting member 132.
- lithium nickelate is used as the positive electrode active material 153.
- a natural graphite-based carbon material is used as the negative electrode active material 154.
- nonaqueous electrolyte solution 140 non-aqueous electrolyte obtained by dissolving lithium hexafluorophosphate (LiPF 6 ) in a nonaqueous solvent obtained by mixing EC (ethylene carbonate), DMC (dimethyl carbonate), and EMC (ethyl methyl carbonate).
- EC ethylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- step S1 it is determined whether or not the storage amount of the lithium ion secondary battery 100 has decreased to a first specified value (in the first embodiment, the storage amount corresponding to SOC 30%). Specifically, based on the inter-terminal voltage V detected by the voltage detection means 40 by the battery controller 30 (specifically, the average value of the lithium ion secondary battery 100 constituting the assembled battery 10), the lithium ion secondary The storage amount of the secondary battery 100 is calculated, and the SOC (State Of Charge) of the lithium ion secondary battery 100 is estimated from the calculated storage amount.
- a first specified value in the first embodiment, the storage amount corresponding to SOC 30%.
- step S1 When it is determined in step S1 that the storage amount of the lithium ion secondary battery 100 has not decreased to the first specified value (the storage amount corresponding to SOC 30% in the first embodiment) (No). The process ends without starting charging.
- the accelerator pedal is not depressed, and the vehicle speed is “0”, it is determined that the hybrid vehicle 1 is in the stopped state, and the stop state signal is transmitted to the battery controller 30. Send to. Therefore, when the battery controller 30 detects a stop state signal from the ECU 60, it determines that the hybrid vehicle 1 is in a stop state.
- step S2 If it is determined in step S2 that the hybrid vehicle 1 is not in a stopped state (No), the process returns to step S1 and the above-described processing is performed.
- step S3 when it is determined that the engine 3 is not operating (No), the process proceeds to step S4 to instruct the operation of the engine 3.
- the engine 3 enters an operating state (idling state), and the generator 9 (alternator) is driven accordingly.
- step S5 charging of the lithium ion secondary battery 100 constituting the assembled battery 10 is started. Specifically, in a state where the generator 9 is driven by the operation of the engine 3, the electric power generated by the generator 9 is supplied to the lithium ion secondary battery 100 constituting the assembled battery 10. In Example 1, the current is made constant at 8C (40 A) and supplied to the lithium ion secondary battery 100.
- step S6 it is determined whether or not the first split charging period KC1 has elapsed.
- the length tc of the first divided charging period KC1 is 67.5 seconds. Therefore, it is determined whether 67.5 seconds have elapsed since the start of charging.
- each lithium ion secondary battery 100 can be charged with an amount of electricity (0.75 Ah) corresponding to SOC 15%. Therefore, in the first embodiment, the lithium ion secondary battery 100 in which the SOC has decreased to 30% can be recovered to 45% SOC in the first divided charging period (67.5 seconds).
- step S6 If it is determined in step S6 that the first split charging period KC1 has not elapsed (No), this process is repeated until the first split charging period KC1 has elapsed. Thereafter, when it is determined in step S6 that the first split charging period KC1 has elapsed (Yes), the process proceeds to step S7, and charging of the lithium ion secondary battery 100 is suspended.
- step S8 it is determined whether or not the charging suspension period KR has elapsed.
- the length tr of the charging suspension period KR is 30 seconds. Therefore, it is determined whether or not 30 seconds have elapsed since charging was suspended. If it is determined in step S8 that the charging suspension period has not elapsed (No), this process is repeated until the charging suspension period KR has elapsed. Thereafter, when it is determined in step S8 that the charging suspension period KR has elapsed (Yes), the process proceeds to step S9, and charging of the lithium ion secondary battery 100 is resumed.
- step SA it is determined whether or not the storage amount of the lithium ion secondary battery 100 has reached a second specified value (the storage amount corresponding to SOC 60% in the first embodiment). Specifically, based on the inter-terminal voltage V detected by the voltage detection means 40 by the battery controller 30 (specifically, the average value of the lithium ion secondary battery 100 constituting the assembled battery 10), the lithium ion secondary The storage amount of the secondary battery 100 is calculated, and the SOC of the lithium ion secondary battery 100 is estimated from the calculated storage amount. Then, based on the estimated SOC, it is determined whether or not the storage amount of the lithium ion secondary battery 100 has reached the second specified value. In the first embodiment, if the estimated SOC has reached 60%, it can be determined that the charged amount of the lithium ion secondary battery 100 has reached the second specified value.
- the lithium ion secondary battery 100 is charged with a constant current of 8C (40 A) in the first divided charging period KC1 and the second divided charging period KC2. Therefore, the length tc of the second divided charging period KC2 is also 67.5 seconds, the same as the length of the first divided charging period.
- the charged amount of the lithium ion secondary battery 100 is set to the second specified value (SOC60) after charging is resumed in step S9 for the lithium ion secondary battery 100 that has been recovered to SOC 45%. This corresponds to the period until the amount of stored electricity corresponding to%) is reached.
- step SA when it is determined that the amount of power stored in the lithium ion secondary battery 100 has not reached the second specified value (No), this process is repeated until it reaches the second specified value. Thereafter, in step SA, when it is determined that the charged amount of the lithium ion secondary battery 100 has reached the second specified value (Yes), the charging is terminated.
- charging by performing the processes of steps S7 and S8, charging can be suspended within the period of charging from the first specified value (SOC 30%) to the second specified value (SOC 60%). it can.
- SOC 30% the first specified value
- SOC 60% the second specified value
- Li ions staying at the interface between the electrolytic solution and the negative electrode can be diffused by diffusion control, so that metal Li is deposited on the negative electrode surface. Can be suppressed. Thereby, the fall of the electrical capacity accompanying precipitation of metal Li can be suppressed.
- the length tc of each divided charging period is 40 seconds or more (specifically, 67.5 seconds). In this way, by increasing the length of one split charging period, idling of the hybrid vehicle 1 can be stabilized even during the charging period, so that ride comfort is not impaired.
- steps S5 to SA correspond to a charging step.
- Example 1 A lithium ion secondary battery 100 having a storage amount corresponding to SOC 30% is prepared, and charging is performed in a temperature environment of 15 ° C. until the SOC is restored to 60% as described above. Specifically, after charging for 67.5 seconds at a constant current of 40A (8C), it is paused for 30 seconds, and then charged for 67.5 seconds at a constant current of 40A (8C). Thereby, the storage amount of the lithium ion secondary battery 100 can be recovered to the storage amount corresponding to SOC 60%.
- the lithium ion secondary battery 100 is discharged with a constant current of 20A (4C), and the amount of charge of the lithium ion secondary battery 100 is reduced to the amount of charge corresponding to SOC 30%.
- This charging / discharging cycle was made into 1 cycle, and 128 charging / discharging cycles were performed.
- the discharge capacities at the 40th, 68th, 89th and 128th cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%).
- the capacity maintenance ratios in each cycle were 99.67%, 99.49%, 99.31%, and 98.53%, respectively.
- This result is shown by a one-dot chain line in FIG. 8 as the relationship between the number of charge / discharge cycles and the capacity retention rate.
- the number of divided charging periods is 2
- the length tc of the divided charging period is 67.5 seconds
- Comparative Example 1 a cycle test according to Comparative Example 1 was performed.
- charging was performed continuously without dividing the charging period. Specifically, by continuously charging with a constant current of 40 A (8 C) for 135 seconds, the storage amount of the lithium ion secondary battery 100 is recovered to the storage amount corresponding to SOC 60%, and then 20 A (4 C The lithium ion secondary battery 100 was discharged with a constant current of) to reduce the charged amount of the lithium ion secondary battery 100 to a charged amount corresponding to SOC 30%.
- This charging / discharging cycle was made into 1 cycle, and 117 charging / discharging cycles were performed.
- the discharge capacities at the 16th, 45th, 81st, and 117th cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%).
- the capacity maintenance ratio in each cycle was 99.75%, 99.42%, 98.93%, and 97.78% in this order.
- the test results are shown by broken lines in FIG.
- the charging period from the first specified value to the second specified value includes two or more divided charging periods and a charging suspension period (non-charging period) between each divided charging period. It can be said that it was divided into two. Thus, it is considered that Li ions staying at the interface between the electrolytic solution and the negative electrode could be diffused by the diffusion-controlled rate in the lithium ion secondary battery 100 by stopping the charging in the middle of the charging period. Thereby, it can be said that the fall of the electric capacity accompanying precipitation of metal Li could be suppressed.
- Example 2 when the results of Example 1 and Example 2 were compared, the decrease in capacity retention rate of Example 2 was even smaller than that of Example 1. This is probably because the number of split charging periods is larger in the second embodiment than in the first embodiment, and the number of charging suspension periods during that period is also large (the total charging period is also longer). From this result, it can be said that the suppression effect of the electric capacity fall accompanying precipitation of metal Li can be heightened, so that the number of split charging periods is increased.
- Examples 3 to 5 and Comparative Example 2 In the third to fifth embodiments, unlike the first embodiment, the number of divided charging periods is changed to 6, the divided charging period length tc is changed to 60 seconds, and the charging current is changed to a constant current of 15A (3C). The secondary battery 100 was charged. For discharging, a cycle test was conducted in the same manner as in Example 1. However, in Examples 3 to 5, the length tc of the charging suspension period is different from each other. Further, the discharge current is changed to a constant current of 7.5 A (1.5 C).
- Comparative Example 2 For comparison with Examples 3 to 5, a cycle test according to Comparative Example 2 was performed. In Comparative Example 2, unlike Examples 3 to 5, charging was performed continuously without dividing the charging period. Specifically, by continuously charging with a constant current of 15A (3C) for 360 seconds, the storage amount of the lithium ion secondary battery 100 is restored to the storage amount corresponding to SOC 60%, and then 20A (4C The lithium ion secondary battery 100 was discharged with a constant current of) to reduce the charged amount of the lithium ion secondary battery 100 to a charged amount corresponding to SOC 30%. This charging / discharging cycle was made into 1 cycle, and 1838 charging / discharging cycles were performed.
- the charging period from the first specified value to the second specified value is divided into two or more divided charging periods and a charging suspension period (non-charging period) between each divided charging period. It can be said that it was divided into two.
- Example 4 the capacity retention rate increases in the order of Example 3, Example 4, and Example 5. This is because even if the number of divided charging periods is equal (that is, the number of charging suspension periods is equal), the length tr of the charging suspension period is different (tr is increased in order). it is conceivable that. From this result, even if the number of divided charging periods is equal (even if the number of charging suspension periods is the same), as the length tr of the charging suspension period is increased, the effect of suppressing the decrease in electric capacity accompanying the deposition of metal Li It can be said that it can raise.
- Example 6 to 8 Comparative Example 3
- the test environment temperature was changed to 0 ° C., and the cycle test was performed.
- the length tc of the charging suspension period is sequentially changed to 10 seconds, 30 seconds, and 60 seconds.
- the discharge is the same as in the first embodiment.
- Comparative Example 3 For comparison with Examples 6 to 8, a cycle test according to Comparative Example 3 was performed. In Comparative Example 3, unlike Examples 6 to 8, charging was performed continuously without dividing the charging period. For discharging, 889 charge / discharge cycles were performed in the same manner as in Examples 6-8. At this time, the discharge capacities at the 15, 55, 161, 282, 351, 516, and 889 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%). The capacity retention ratio in each cycle was 99.62%, 99.29%, 98.49%, 97.8%, 97.12%, 95.64%, and 87.8% in this order. The test results are shown by broken lines in FIG.
- the charging suspension period is made too long with respect to the divided charging period, the charged amount of the lithium ion secondary battery 100 is reduced to the second specified value (in the first to eighth embodiments, the SOC 60) while the hybrid vehicle 1 is stopped. There is a risk that it will not be possible to recover the amount of stored electricity corresponding to%).
- the charging suspension period is sufficient to allow diffusion of Li ions staying at the interface between the electrolyte and the negative electrode due to diffusion control, and further charging suspension is wasted.
- Example 8 when the test results of Example 7 and Example 8 are examined in detail, the capacity retention rate of Example 8 is larger than Example 7 up to about 600 cycles, but the difference is slight.
- Example 8 since the length tc of the divided charging period is 67.5 seconds and the length tr of the charging suspension period is 60 seconds, tr / tc is about 0.9. From this, even if the charging suspension period is made longer than that in Example 8 and tr / tc is made larger than 0.9, the charging period K for recovering the charged amount of the lithium ion secondary battery 100 to the second specified value. It can be said that the effect of increasing the capacity retention rate is extremely small simply by increasing the length of the battery.
- the ratio tr / tc between the length tc of each divided charging period and the length tr of the charging suspension period immediately thereafter is preferably 0.9 or less.
- Example 9 and 10 In Examples 9 and 10, as in Examples 6 to 8, the test environment temperature was changed to 0 ° C., and the cycle test was performed. However, in Examples 9 and 10, the length tc of the charging suspension period is sequentially changed to 1 second and 5 seconds.
- Example 6 and Comparative Example 3 are shown by a one-dot chain line and a broken line in FIG. 11, respectively.
- tr / tc of Comparative Example 3, Example 9, Example 10, and Example 6 are 0, 0.015, 0.074, and 0.148 in this order.
- the ratio tr / tc between the length tc of each divided charging period and the length tr of the charging suspension period immediately after that is preferably 0.14 or more.
- Example 11 and 12 and Comparative Example 4 In Examples 11 and 12, unlike Example 1, the test environment temperature was set to ⁇ 15 ° C., the charging current was set to a constant current of 20 A (4 C), and the length tc of the divided charging period was set to 136.5 seconds and 91 seconds. Changed to and charged. For discharging, a cycle test was conducted in the same manner as in Example 1. However, in Examples 11 and 12, the number of divided charging periods is different from each other. Further, the discharge current is changed to a constant current of 10A (2C).
- Comparative Example 4 For comparison with Examples 11 and 12, a cycle test according to Comparative Example 4 was performed.
- charging was performed continuously without dividing the charging period.
- About discharge it carried out similarly to Examples 11 and 12, and performed 531 charge / discharge cycles.
- the discharge capacities at the 45th, 118th, 214th, 254th, 374th and 531st cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance ratio (%).
- the capacity retention ratio in each cycle was 99.34%, 98.95%, 97.89%, 97.17%, 94.9%, and 90.49% in this order.
- the test results are shown by broken lines in FIG.
- the decrease in capacity retention rate associated with the cycle test was smaller than in Comparative Example 4.
- the charging period from the first specified value to the second specified value is divided into two or more divided charging periods and a charging suspension period (non-charging period) between each divided charging period. It can be said that it was divided into two.
- Example 12 when comparing the results of Example 11 and Example 12, the decrease in capacity retention rate of Example 12 was even smaller than that of Example 11. This is probably because the number of divided charging periods is larger in Example 12 than in Example 11, and the number of charging suspension periods during that period is also large (the total charging period is also longer). From this result, it can be said that the suppression effect of the electric capacity fall accompanying precipitation of metal Li can be heightened, so that the number of division
- Example 13 and 14 and Comparative Example 5 Next, unlike the above-described Example 1 and the like, the second specified value was changed to a storage amount corresponding to SOC 50%, and the cycle tests according to Examples 13 and 14 and Comparative Example 5 were performed.
- the test environment temperature was ⁇ 15 ° C.
- the charging current was a constant current of 10 A (2C)
- the length tc of the divided charging period was 60 seconds
- the divided charging period was The cycle test was performed with the number changed to six.
- the length tr of the charging suspension period is varied.
- the discharge current is changed to a constant current of 5A (1C).
- Comparative Example 5 For comparison with Examples 13 and 14, a cycle test according to Comparative Example 5 was performed.
- charging was performed continuously without dividing the charging period.
- About discharge it carried out similarly to Example 13 and 14, and performed 1531 charge / discharge cycles.
- the discharge capacities at 150, 496, 666, 872, 1110, 1329, and 1531 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%).
- the capacity retention ratio in each cycle was 99.59%, 99.24%, 98.95%, 98.43%, 97.92%, 97.43%, and 96.58% in this order.
- the test results are shown by broken lines in FIG.
- the decrease in capacity retention rate associated with the cycle test was smaller than in Comparative Example 5.
- the charging period from the first specified value to the second specified value is divided into two or more divided charging periods and a charging suspension period (non-charging period) between each divided charging period. It can be said that it was divided into two.
- Example 14 Furthermore, comparing the test results of Examples 13 and 14, the capacity retention rate of Example 14 is larger than that of Example 13. This is because the number of split charging periods is the same in the thirteenth embodiment and the fourteenth embodiment (that is, the number of charging suspension periods is the same), but the charging suspension of the fourteenth embodiment is shorter than that of the thirteenth embodiment. This is probably because the length tr of the period is increased. From this result, even if the number of divided charging periods is equal (even if the number of charging suspension periods is the same), as the length tr of the charging suspension period is increased, the effect of suppressing the decrease in electric capacity accompanying the deposition of metal Li It can be said that it can raise.
- the non-charging period is the discharging period. That is, discharging is performed over the entire non-charging period.
- the battery controller 30 divides the charging period until the charged amount of the lithium ion secondary battery 100 reaches the second specified value into three divided charging periods (first to third divided charging periods), respectively. It is divided into a non-charging period between the divided charging periods. Then, charging is performed during the divided charging period and discharging is performed during the non-charging period. That is, “charging, discharging, charging, discharging, charging” is performed to recover the amount of stored electricity to the second specified value.
- step U5 charging of the lithium ion secondary battery 100 constituting the assembled battery 10 is started. Specifically, in a state where the generator 9 is driven by the operation of the engine 3, the electric power generated by the generator 9 is supplied to the lithium ion secondary battery 100 constituting the assembled battery 10. In Example 15, the current is kept constant at 3C (15A) and supplied to the lithium ion secondary battery 100.
- step U52 determines whether or not the first split charging period has elapsed.
- the length of the first divided charging period is 120 seconds. Therefore, it is determined whether 120 seconds have elapsed since the start of charging.
- each lithium ion secondary battery 100 can be charged with an amount of electricity (0.5 Ah) corresponding to 10% of SOC. Therefore, in the fifteenth embodiment, the lithium ion secondary battery 100 whose SOC is reduced to 30% in the first divided charging period (120 seconds) can be recovered to SOC 40%.
- step U52 If it is determined in step U52 that the first split charging period has not elapsed (No), this process is repeated until the first split charging period has elapsed. Thereafter, when it is determined in step U52 that the first split charging period has elapsed (Yes), the process proceeds to step U53, where charging of the lithium ion secondary battery 100 is stopped and discharging is started. In the fifteenth embodiment, discharging is performed with a constant current of 7.5A.
- step U54 determines whether or not the discharge period has elapsed.
- the length of the discharge period is 0.5 seconds. Therefore, it is determined whether 0.5 second has elapsed since the start of discharge. If it is determined in step U54 that the discharge period has not elapsed (No), this process is repeated until the discharge period elapses. Thereafter, when it is determined in step U54 that the discharge period has elapsed (Yes), the process proceeds to step U55, and charging of the lithium ion secondary battery 100 is resumed.
- step U56 determines whether or not the second split charging period has elapsed.
- the length of the second divided charging period is 120 seconds. Therefore, it is determined whether 120 seconds have elapsed since the start of charging.
- each lithium ion secondary battery 100 can be charged with an amount of electricity (0.5 Ah) corresponding to 10% of SOC. Therefore, in the fifteenth embodiment, the lithium ion secondary battery 100 with 40% SOC can be recovered to 50% SOC in the second divided charging period (120 seconds).
- step U56 If it is determined in step U56 that the second divided charging period has not elapsed (No), this process is repeated until the second divided charging period has elapsed. Thereafter, when it is determined in step U56 that the second split charging period has elapsed (Yes), the process proceeds to step U57, where charging of the lithium ion secondary battery 100 is stopped and discharging is started. Again, discharging is performed at a constant current of 7.5A.
- step U58 it is determined whether or not the discharge period has elapsed. Again, the length of the discharge period is 0.5 seconds. Therefore, it is determined whether 0.5 second has elapsed since the start of discharge. If it is determined in step U58 that the discharge period has not elapsed (No), this process is repeated until the discharge period elapses. Thereafter, when it is determined in step U58 that the discharge period has elapsed (Yes), the process proceeds to step U59, and charging of the lithium ion secondary battery 100 is resumed.
- step U5A the charged amount of the lithium ion secondary battery 100 is set to the second specified value (the charged amount corresponding to SOC 60% in the fifteenth embodiment) as in step SA of the first embodiment. It is determined whether it has been reached. Also in the fifteenth embodiment, if the estimated SOC has reached 60%, it can be determined that the stored amount of the lithium ion secondary battery 100 has reached the second specified value.
- Example 15 the lithium ion secondary battery 100 is charged with a constant current of 3C (15A) in the first, second, and third divided charging periods. Accordingly, the length of the third divided charging period is also 120 seconds, the same as the length of the first divided charging period.
- the lithium ion secondary battery 100 that has been recovered to SOC 50% is charged again in step U59, and then the charged amount of the lithium ion secondary battery 100 is the second specified value (SOC 60%). This corresponds to the period until the amount of stored electricity corresponding to
- step U5A when it is determined that the charged amount of the lithium ion secondary battery 100 has not reached the second specified value (No), this process is repeated until it reaches the second specified value. Thereafter, in step U5A, when it is determined that the charged amount of the lithium ion secondary battery 100 has reached the second specified value (Yes), the process returns to the main routine of FIG.
- steps U51 to U5A correspond to charging steps.
- Example 16 differs from Example 15 only in the length of the discharge period, and is otherwise the same. Specifically, in Example 16, the length of each discharge period is set to 1.0 second, and the lithium ion secondary battery 100 is charged (Steps U51 to U5A).
- the non-charging period is a charging suspension period and a discharging period. That is, charging is stopped and discharged in each non-charging period.
- the battery controller 30 divides the charging period until the charged amount of the lithium ion secondary battery 100 reaches the second specified value into three divided charging periods (first to third divided charging periods), respectively. It is divided into a non-charging period between the divided charging periods. Then, charging is performed during each divided charging period, and charging suspension and discharging are performed during each non-charging period. That is, “charge, pause, discharge, charge, pause, discharge, charge” is performed to restore the stored amount of electricity to the second specified value.
- step V5 charging of the lithium ion secondary battery 100 constituting the assembled battery 10 is started. Specifically, in a state where the generator 9 is driven by the operation of the engine 3, the electric power generated by the generator 9 is supplied to the lithium ion secondary battery 100 constituting the assembled battery 10. Also in Example 17, the current is kept constant at 3C (15A) and supplied to the lithium ion secondary battery 100.
- step V52 determines whether or not the first split charging period has elapsed. Also in the seventeenth embodiment, the length of the first divided charging period is 120 seconds. Therefore, it is determined whether 120 seconds have elapsed since the start of charging.
- each lithium ion secondary battery 100 can be charged with an amount of electricity (0.5 Ah) corresponding to 10% of SOC. Therefore, also in the present Example 17, the lithium ion secondary battery 100 in which the SOC is reduced to 30% in the first divided charging period (120 seconds) can be recovered to 40% SOC.
- step V52 If it is determined in step V52 that the first split charging period has not elapsed (No), this process is repeated until the first split charging period has elapsed. Thereafter, when it is determined in step V52 that the first split charging period has elapsed (Yes), the process proceeds to step V53, and charging of the lithium ion secondary battery 100 is suspended.
- step V54 determines whether or not the charging suspension period has elapsed.
- the length of the charging suspension period is 30 seconds. Therefore, it is determined whether or not 30 seconds have elapsed since charging was suspended. If it is determined in step V54 that the charging suspension period has not elapsed (No), this process is repeated until the charging suspension period elapses. Thereafter, when it is determined in step V54 that the charging suspension period has elapsed (Yes), the process proceeds to step V55, and discharging of the lithium ion secondary battery 100 is started. Also in Example 17, discharge is performed at a constant current of 7.5A.
- step V56 determines whether or not the discharge period has elapsed.
- the length of the discharge period is 1.0 second. Therefore, it is determined whether 1.0 second has elapsed since the start of discharge. If it is determined in step V56 that the discharge period has not elapsed (No), this process is repeated until the discharge period elapses. Thereafter, when it is determined in step V56 that the discharge period has elapsed (Yes), the process proceeds to step V57, and charging of the lithium ion secondary battery 100 is resumed.
- step V58 determines whether or not the second split charging period has elapsed. Also in the embodiment 17, the length of the second divided charging period is 120 seconds. Therefore, it is determined whether 120 seconds have elapsed since the resumption of charging.
- each lithium ion secondary battery 100 can be charged with an amount of electricity (0.5 Ah) corresponding to 10% of SOC. Therefore, also in the present Example 17, the lithium ion secondary battery 100 with 40% SOC can be recovered to 50% SOC in the second divided charging period (120 seconds).
- step V58 If it is determined in step V58 that the second divided charging period has not elapsed (No), this process is repeated until the second divided charging period has elapsed. Thereafter, when it is determined in step V58 that the second split charging period has elapsed (Yes), the process proceeds to step V59, and charging of the lithium ion secondary battery 100 is suspended.
- step V5A it is determined whether or not the charging suspension period has elapsed. Again, the length of the charging suspension period is 30 seconds. Therefore, it is determined whether or not 30 seconds have elapsed since charging was suspended. If it is determined in step V5A that the charging suspension period has not elapsed (No), this process is repeated until the charging suspension period has elapsed. Thereafter, when it is determined in step V5A that the charging suspension period has elapsed (Yes), the process proceeds to step V5B, and discharging of the lithium ion secondary battery 100 is started. Again, discharging is performed at a constant current of 7.5A.
- step V5C it is determined whether or not the discharge period has elapsed. Again, the length of the discharge period is 1.0 seconds. Therefore, it is determined whether 1.0 second has elapsed since the start of discharge. If it is determined in step V5C that the discharge period has not elapsed (No), this process is repeated until the discharge period elapses. Thereafter, when it is determined in step V5C that the discharge period has elapsed (Yes), the process proceeds to step V5D, and charging of the lithium ion secondary battery 100 is resumed.
- step V5E the charged amount of the lithium ion secondary battery 100 is set to the second specified value (the charged amount corresponding to SOC 60% in the present example 17) as in step SA of the example 1. It is determined whether it has been reached. Also in the present Example 17, if the estimated SOC has reached 60%, it can be determined that the stored amount of the lithium ion secondary battery 100 has reached the second specified value.
- the lithium ion secondary battery 100 is charged with a constant current of 3C (15A) during the first divided charging period to the third divided charging period. Accordingly, the length of the third divided charging period is also 120 seconds, the same as the length of the first divided charging period.
- the charged amount of the lithium ion secondary battery 100 is the second specified value (SOC 60%). This corresponds to the period until the amount of stored electricity corresponding to
- step V5E when it is determined that the amount of power stored in the lithium ion secondary battery 100 has not reached the second specified value (No), this process is repeated until it reaches the second specified value. Thereafter, when it is determined in step V5E that the charged amount of the lithium ion secondary battery 100 has reached the second specified value (Yes), the process returns to the main routine of FIG. In the seventeenth embodiment, steps V51 to V5E correspond to the charging step.
- the lithium ion secondary battery 100 is charged from the first specified value (amount of storage corresponding to SOC 30%) to a second specified value (amount of storage corresponding to SOC 60%), and then discharged to the first specified value.
- a cycle test was conducted with one charge / discharge cycle. This cycle test will be described in detail below.
- a lithium ion secondary battery 100 having a storage amount corresponding to SOC 30% is prepared, and charged in a temperature environment of ⁇ 15 ° C. as described above until the SOC recovers to 60% (Steps U51 to U5A). )I do. Thereafter, the lithium ion secondary battery 100 is discharged with a constant current of 20A (4C), and the amount of charge of the lithium ion secondary battery 100 is reduced to the amount of charge corresponding to SOC 30%.
- This charge / discharge cycle was defined as 1 cycle, and 1124 cycles of charge / discharge cycles were performed.
- the discharge capacities at 101, 295, 496, 708, 915 and 1124 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity retention rate (%).
- the capacity retention ratio in each cycle was 99.54%, 99.01%, 98.61%, 98.14%, 97.23%, and 96.04% in this order. This result is shown by a one-dot chain line and a black triangle in FIG. 17 as the relationship between the number of charge / discharge cycles and the capacity retention rate.
- Example 16 unlike Example 15, the length of the discharge period was changed to 1.0 second and the lithium ion secondary battery 100 was charged (Steps U51 to U5A). Other than that was carried out similarly to Example 15, and performed 1097 charge-discharge cycles. At this time, the discharge capacities at 101,294,496,704,913,1097 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%). The capacity retention ratio in each cycle was 99.34%, 99.03%, 98.83%, 98.41%, 97.78%, and 97.13% in this order. The test results are shown in FIG. 17 by a two-dot chain line and a black diamond.
- Example 17 unlike Example 15, the processes of Steps V51 to V5E were performed to charge the lithium ion secondary battery 100. Other than that was carried out similarly to Example 15, and performed 1068 charge / discharge cycles.
- the discharge capacities at the 80th, 238th, 401th, 568th, 733th, 903th and 1068th cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%).
- the capacity retention ratio in each cycle was 99.86%, 99.83%, 99.52%, 99.35%, 98.98%, 98.76%, and 98.28% in this order.
- the test results are shown by solid lines and white squares in FIG.
- Comparative Example 6 For comparison with Examples 15 to 17, a cycle test according to Comparative Example 6 was performed. In Comparative Example 6, unlike Examples 15 to 17, charging was performed continuously without dividing the charging period. Specifically, by continuously charging with a constant current of 15A (3C) for 360 seconds, the storage amount of the lithium ion secondary battery 100 is restored to the storage amount corresponding to SOC 60%, and then 20A (4C The lithium ion secondary battery 100 was discharged with a constant current of) to reduce the charged amount of the lithium ion secondary battery 100 to a charged amount corresponding to SOC 30%. This charging / discharging cycle was made into 1 cycle, and 1134 charging / discharging cycles were performed.
- the discharge capacities at the 103, 298, 500, 713, 921, and 1134 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance ratio (%).
- the capacity retention ratio in each cycle was 99.44%, 98.88%, 98.42%, 97.58%, 96.43%, and 95.27% in this order.
- the test results are indicated by broken lines and black circles in FIG.
- Example 15 and 16 the decrease in capacity maintenance rate accompanying the cycle test was smaller than that in Comparative Example 6.
- the charging period from the first specified value to the second specified value is divided into three divided charging periods and a discharging period (non-charging period) between each divided charging period. It can be said that. In this way, it is considered that by discharging in the middle of the charging period, Li ions staying at the interface between the electrolytic solution and the negative electrode could be diffused by the diffusion-controlled rate in the lithium ion secondary battery 100. . Thereby, it can be said that the fall of the electric capacity accompanying precipitation of metal Li could be suppressed.
- Example 17 as compared with Comparative Example 6, the decrease in the capacity maintenance rate accompanying the cycle test (repetition of charge / discharge) was reduced.
- the charging period from the first specified value to the second specified value is divided into three divided charging periods, and a non-charging period (charging suspension period and discharging period) between each divided charging period. It can be said that it was divided into two. In this way, by performing the pause and discharge in the middle of the charging period, Li ions staying at the interface between the electrolytic solution and the negative electrode can be diffused by the diffusion-controlled rate in the lithium ion secondary battery 100. Conceivable. Thereby, it can be said that the fall of the electric capacity accompanying precipitation of metal Li could be suppressed.
- Example 16 when comparing the results of Example 15 and Example 16, the decrease in capacity retention rate of Example 16 was even smaller than that of Example 15. This is probably because the discharge period of Example 16 is longer than that of Example 15. From this result, it can be said that by increasing the discharge period, it is possible to enhance the effect of suppressing the decrease in electric capacity accompanying the precipitation of metal Li.
- Example 17 when the results of Example 16 and Example 17 were compared, the decrease in capacity retention rate in Example 17 was even smaller than that in Example 16. This is considered to be because in Example 17, the same discharge as in Example 16 is performed in the non-charging period, but in addition to this, a charging suspension period is provided. From this result, it can be said that by performing charging suspension and discharging in each non-charging period, it is possible to further enhance the effect of suppressing the decrease in electric capacity accompanying the deposition of metal Li, compared with the case where only discharging is performed. .
- Example 1 Next, a method for charging a lithium ion secondary battery according to Modification 1 will be described.
- the first split charging period KC1 is set to 67.5 seconds, and it is determined whether 67.5 seconds have elapsed since the start of charging in step S5.
- step T ⁇ b> 6 is set, and it is determined whether or not the charged amount of the lithium ion secondary battery 100 has reached the specified division value.
- the division specified value is an intermediate value between the first specified value (amount of storage corresponding to SOC 30%) and a second specified value (amount of storage corresponding to SOC 60%). Set to quantity.
- the estimated SOC estimated by the battery controller 30 reaches 45%, it can be determined that the charged amount of the lithium ion secondary battery 100 has reached the specified division value. If it is determined in step T6 that the charged amount of the lithium ion secondary battery 100 has reached the specified division value, charging is suspended in step S7. Thereafter, similarly to Example 1, the processes of Steps S8 to SA are performed, and the charged amount of the lithium ion secondary battery 100 is recovered to the second specified value.
- the charging period in which charging is performed until the amount of stored power that has decreased to the first specified value reaches the second specified value is divided into two divided charging periods and a non-charging period (charging suspension period) between them. And charging during the divided charging period, and charging can be suspended during the non-charging period.
- Li ions staying at the interface between the electrolyte and the negative electrode can be diffused by the diffusion rate control. It can suppress that metal Li precipitates on the surface. Thereby, the fall of the electrical capacity accompanying precipitation of metal Li can be suppressed.
- the length tc of each divided charging period can be 40 seconds or more.
- the amount of electricity (0.75 Ah) corresponding to SOC 15% at a constant current of 8C (40A) The lithium ion secondary battery 100 is charged. Therefore, the length tc of each divided charging period is 67.5 seconds. In this way, by increasing the length of one split charging period, idling of the hybrid vehicle 1 can be stabilized even during the charging period, so that ride comfort is not impaired.
- the storage amount of the lithium ion secondary battery 100 is used as the first specified value, the second specified value, and the divided specified value. It may be used.
- the voltage V between terminals of the lithium ion secondary battery 100 is a voltage value between terminals corresponding to a first specified value (a charged amount corresponding to SOC 30%). It may be determined whether or not the voltage has decreased to V1).
- the ROM 31 of the battery controller 30 stores The terminal-to-terminal voltage value V1 when the SOC is 30% is stored as the first specified value. Thereby, when the voltage detection means 40 detects the inter-terminal voltage value V1, the battery controller 30 determines that the inter-terminal voltage V of the lithium ion secondary battery 100 has decreased to the first specified value. be able to. Similarly, in step SA in FIGS. 7 and 14 and steps U5A and V5E in FIGS.
- the voltage V between terminals of the lithium ion secondary battery 100 is the second specified value (SOC 60% storage state). It may be determined whether or not the inter-terminal voltage value V2) is reached. Further, in step T6 of FIG. 14, it is determined whether or not the inter-terminal voltage V of the lithium ion secondary battery 100 has reached a specified division value (inter-terminal voltage value V3 when the SOC is 45%).
- step SA it is determined whether or not the charged amount of the lithium ion secondary battery 100 has reached the second specified value (see FIG. 7). You may make it determine whether the division
- both the first divided charging period KC1 and the second divided charging period KC2 were charged with the same constant current (specifically, 40 A).
- the first divided charging period KC1 and the second divided charging period KC2 may be charged with a constant current with different current values.
- the battery temperature of the lithium ion secondary battery 100 may be detected, and charging may be performed by changing the current value according to the change in the battery temperature.
- Examples 15 and 17 it was determined in steps U52 and V52 whether or not the first split charging period had elapsed (see FIGS. 16 and 18). Specifically, the length of the first divided charging period is set to 120 seconds, and in steps U52 and V52, it is determined whether or not 120 seconds have elapsed since the start of charging.
- the first division regulation value is set to the amount of stored electricity corresponding to SOC 40%.
- the process may proceed to steps U53 and V53.
- steps U56 and V58 it may be determined whether or not the storage amount of the lithium ion secondary battery 100 has reached the second division regulation value.
- the second division specified value is set to an amount of stored electricity corresponding to SOC 50%.
- the process may proceed to steps U57 and V59.
- Example 1 charging of the lithium ion secondary battery 100 was temporarily suspended with the non-charging period as the charging suspension period.
- the lithium ion secondary battery 100 may be temporarily discharged using the non-charging period as a discharging period.
- the cycle test according to Reference Examples 1 to 4 will be described.
- the lithium ion secondary battery 100 is charged at a constant current of 80 A (16 C) at a constant current of 80 A (16 C) until reaching a final voltage of 4.3 V, and then charged at a constant voltage of 4.3 V. Charge to about 100% SOC. Then, it rests for 180 seconds.
- the battery is discharged at a constant current of 1 A until it reaches a final voltage of 3.726 V, and then discharged at a constant voltage of 3.726 V, so that the SOC is adjusted to about 60%. Then, it rests for 420 seconds.
- This charge / discharge cycle was defined as one cycle, and 3092 cycles were performed.
- the discharge capacities of the 200, 482, 861, 1389, 2049, 2702, and 3092 cycles were measured, and the ratio to the initial capacity was calculated as the capacity maintenance rate (%).
- the capacity retention ratio in each cycle was 99.69%, 99.08%, 98.26%, 97.15%, 95.07%, 92.52%, and 91.63% in this order. This result is shown by a broken line and a black circle in FIG. 19 as the relationship between the number of cycles and the capacity retention rate.
- the reference example 2 differs from the reference example 1 only in that the discharge is performed for 1 second at a constant current of 5 A before each cycle charge / discharge.
- a test was conducted. At this time, the discharge capacities at the 650th, 1412th, 2166th, 2528th, and 2944th cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity retention rate (%).
- the capacity maintenance ratio in each cycle was 99.4%, 99.9%, 97.7%, 96.6%, and 94.8% in this order.
- This test result is shown by a one-dot chain line and a black triangle in FIG.
- the reference example 3 is different from the reference example 1 only in that the discharge is performed for 1 second at a constant current of 40 A before each cycle charge / discharge.
- a test was conducted. At this time, the discharge capacities at the 651, 1416, 2172, 2535, and 2951 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity retention rate (%).
- the capacity maintenance ratio in each cycle was 99.4%, 98.8%, 98.1%, 97.4%, and 96.7% in this order.
- the test results are shown in FIG. 19 by solid lines and white squares.
- the reference example 4 is different from the reference example 1 only in that the discharge is performed for 5 seconds at a constant current of 40 A before each cycle charge / discharge.
- a test was conducted. At this time, the discharge capacities at 641, 1395, 2140, 2497, and 2905 cycles were measured, respectively, and the ratio to the initial capacity was calculated as the capacity maintenance ratio (%).
- the capacity retention ratio in each cycle was 99.7%, 99.3%, 98.6%, 98.5%, and 98.4% in this order.
- the test results are shown in FIG. 19 by a two-dot chain line and a black diamond.
- Example 1 the length tr of the charging suspension period was 30 seconds.
- the capacity retention rate could be greatly improved compared to Reference Example 1 even though the discharge time was only 1 second. Therefore, in the charging method of the present invention, by setting the non-charging period as the discharging period, the non-charging period can be greatly shortened as compared with the case where the non-charging period is set as the charging suspension period. It is considered that the decrease in capacity can be further suppressed. Accordingly, by discharging during the non-charging period, the lithium ion secondary battery 100 whose storage amount has been reduced to the first specified value is quickly charged to the second specified value while suppressing a decrease in electric capacity. It is considered possible.
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Abstract
Description
なお、「蓄電量に対応する物理量」とは、蓄電量のほか、蓄電量に1対1で対応する物理量をいい、例えば、SOCや電池電圧(端子間電圧)を挙げることができる。
また、第1規定値としては、SOC30%に相当する蓄電量や、この蓄電状態の電池の端子間電圧値などを例示できる。また、第2規定値としては、SOC60%に相当する蓄電量や、この蓄電状態の電池の端子間電圧値などを例示できる。
これに対し、本発明の充電方法では、各々の分割充電期間の長さtcと、その直後の充電休止期間の長さtrとの比tr/tcを、0.14以上としている。これにより、負極表面に金属Liが析出するのを抑制することができる。
これに対し、本発明の充電方法では、tr/tcを0.9以下としている。これにより、無駄な充電休止時間を費やすことなく、速やかに、リチウムイオン二次電池の蓄電量に対応する物理量の値を第2規定値まで適切に回復させることができる。
しかも、各々の分割充電期間の長さtcと、その直後の充電休止期間の長さtrとの比tr/tcを、0.14以上0.9以下としている。tr/tcを0.14以上とすることで、負極表面に金属Liが析出するのを抑制することができる。さらに、tr/tcを0.9以下とすることで、無駄な充電休止時間を費やすことなく、速やかに、リチウムイオン二次電池の蓄電量に対応する物理量の値を第2規定値まで適切に回復させることができる。
3 エンジン
6 電池システム
9 発電機(オルタネータ)
10 組電池
30 電池コントローラ(第1判定手段、停止状態判定手段、充電制御手段、エンジン稼働判定手段、エンジン稼働指示手段)
40 電圧検知手段
50 電流検知手段
100 リチウムイオン二次電池
153 正極活物質
KC1 第1分割充電期間
KC2 第2分割充電期間
KR 充電休止期間(非充電期間)
次に、本発明の実施例1について、図面を参照しつつ説明する。
本実施例1にかかるハイブリッド自動車1は、図1に示すように、車体2、エンジン3、フロントモータ4、リヤモータ5、電池システム6、ケーブル7、及び発電機9を有し、エンジン3とフロントモータ4及びリヤモータ5との併用で駆動するハイブリッド自動車である。具体的には、このハイブリッド自動車1は、電池システム6をフロントモータ4及びリヤモータ5の駆動用電源として、公知の手段により、エンジン3とフロントモータ4及びリヤモータ5とを用いて走行できるように構成されている。
さらに、電池コントローラ30は、リチウムイオン二次電池100の蓄電量が、第1規定値(本実施例1では、SOC30%に相当する蓄電量)にまで低下しているか否かを判定する。本実施例1では、推定SOCが30%にまで低下しているか否かを判定する。
また、本実施例1では、電池コントローラ30が、第1判定手段、停止状態判定手段、エンジン稼働判定手段、エンジン稼働指示手段、充電制御手段に相当する。
なお、リチウムイオン二次電池100の理論電気容量は、5Ahである。従って、1Cが5Aの電流値になる。
まず、ステップS1において、リチウムイオン二次電池100の蓄電量が、第1規定値(本実施例1では、SOC30%に相当する蓄電量)にまで低下しているか否かを判定する。具体的には、電池コントローラ30により、電圧検知手段40で検知された端子間電圧V(詳細には、組電池10を構成するリチウムイオン二次電池100の平均値)に基づいて、リチウムイオン二次電池100の蓄電量を算出し、算出された蓄電量からリチウムイオン二次電池100のSOC(State Of Charge)を推定する。そして、この推定SOCに基づいて、リチウムイオン二次電池100の蓄電量が、第1規定値にまで低下しているか否かを判定する。本実施例1では、推定SOCが30%にまで低下していれば、リチウムイオン二次電池100の蓄電量が第1規定値にまで低下していると判断することができる。
その後、ステップS6において、第1分割充電期間KC1が経過した(Yes)と判定されると、ステップS7に進み、リチウムイオン二次電池100の充電を休止する。
ステップS8において、充電休止期間が経過していない(No)と判定された場合には、充電休止期間KRが経過するまで、この処理を繰り返す。その後、ステップS8において、充電休止期間KRが経過した(Yes)と判定されると、ステップS9に進み、リチウムイオン二次電池100の充電を再開する。
なお、本実施例1では、ステップS5~SAが充電ステップに相当する。
次に、リチウムイオン二次電池100について、第1規定値(SOC30%に相当する蓄電量)から第2規定値(SOC60%に相当する蓄電量)にまで充電し、その後、第1規定値にまで放電させる充放電サイクルを1サイクルとして、サイクル試験を行った。このサイクル試験について、以下に詳細に説明する。
まず、実施例1にかかるサイクル試験について説明する。SOC30%に相当する蓄電量のリチウムイオン二次電池100を用意し、これについて、15℃の温度環境下において、前述のようにして、SOCが60%に回復するまで充電を行う。具体的には、40A(8C)の定電流で67.5秒間充電した後、30秒間休止し、その後引き続いて、40A(8C)の定電流で67.5秒間充電する。これにより、リチウムイオン二次電池100の蓄電量を、SOC60%に相当する蓄電量にまで回復させることができる。その後、20A(4C)の定電流でリチウムイオン二次電池100を放電させ、リチウムイオン二次電池100の蓄電量をSOC30%に相当する蓄電量にまで低下させる。この充放電サイクルを1サイクルとして、充放電サイクルを128サイクル行った。
なお、実施例1では、分割充電期間の数が2、分割充電期間の長さtcが67.5秒、充電休止期間の長さtrが30秒であるので、tr/tc=30/67.5=0.44となる。
なお、実施例2では、分割充電期間の長さtcが45秒、充電休止期間の長さtrが30秒となり、tr/tc=30/45=0.67となる。
実施例3~5では、実施例1と異なり、分割充電期間の数を6、分割充電期間の長さtcを60秒、充電電流を15A(3C)の定電流に変更して、リチウムイオン二次電池100の充電を行った。放電は、実施例1と同様にして、サイクル試験を行った。但し、実施例3~5では、充電休止期間の長さtcを互いに異ならせている。また、放電電流は、7.5A(1.5C)の定電流に変更している。
実施例6~8では、実施例1と異なり、試験環境温度を0℃に変更して、サイクル試験を行った。但し、実施例6~8では、充電休止期間の長さtcを、順に、10秒、30秒、60秒と異ならせている。なお、放電は、実施例1と同様にしている。
実施例9,10でも、実施例6~8と同様に、試験環境温度を0℃に変更して、サイクル試験を行った。但し、実施例9,10では、充電休止期間の長さtcを、順に、1秒、5秒と異ならせている。
実施例11,12では、実施例1と異なり、試験環境温度を-15℃に、充電電流を20A(4C)の定電流に、分割充電期間の長さtcを136.5秒と91秒とに変更して、充電を行った。放電は、実施例1と同様にして、サイクル試験を行った。但し、実施例11,12では、分割充電期間の数を互いに異ならせている。また、放電電流は、10A(2C)の定電流に変更している。
次に、上述の実施例1等と異なり、第2規定値を、SOC50%に相当する蓄電量に変更して、実施例13,14及び比較例5にかかるサイクル試験を行った。
実施例13,14では、実施例1と異なり、試験環境温度を-15℃に、充電電流を10A(2C)の定電流に、分割充電期間の長さtcを60秒に、分割充電期間の数を6に変更して、サイクル試験を行った。但し、実施例13,14では、充電休止期間の長さtrを異ならせている。また、放電電流は、5A(1C)の定電流に変更している。
実施例15では、実施例1と異なり、非充電期間を放電期間としている。すなわち、非充電期間の全体にわたって放電を行う。
具体的には、電池コントローラ30は、リチウムイオン二次電池100の蓄電量が第2規定値に達するまでの充電期間を、3つの分割充電期間(第1~第3分割充電期間)と、各々の分割充電期間の間の非充電期間とに分割する。そして、分割充電期間に充電を行うと共に、非充電期間に放電を行う。すなわち、「充電、放電、充電、放電、充電」と行って、蓄電量を第2規定値にまで回復させる。
まず、図15に示すように、実施例1と同様に、ステップS1~S4の処理を行う。次いで、ステップU5の充電ルーチンに進む。具体的には、図16に示すように、ステップU51において、組電池10を構成するリチウムイオン二次電池100の充電を開始する。具体的には、エンジン3の稼働により発電機9が駆動している状態で、この発電機9により発電された電力を、組電池10を構成するリチウムイオン二次電池100に供給する。本実施例15では、電流の大きさを3C(15A)で一定として、リチウムイオン二次電池100に供給する。
その後、ステップU52において、第1分割充電期間が経過した(Yes)と判定されると、ステップU53に進み、リチウムイオン二次電池100の充電を停止して放電を開始する。本実施例15では、7.5Aの定電流で放電を行う。
ステップU54において、放電期間が経過していない(No)と判定された場合には、放電期間が経過するまで、この処理を繰り返す。その後、ステップU54において、放電期間が経過した(Yes)と判定されると、ステップU55に進み、リチウムイオン二次電池100の充電を再開する。
その後、ステップU56において、第2分割充電期間が経過した(Yes)と判定されると、ステップU57に進み、リチウムイオン二次電池100の充電を停止して放電を開始する。ここでも、7.5Aの定電流で放電を行う。
ステップU58において、放電期間が経過していない(No)と判定された場合には、放電期間が経過するまで、この処理を繰り返す。その後、ステップU58において、放電期間が経過した(Yes)と判定されると、ステップU59に進み、リチウムイオン二次電池100の充電を再開する。
なお、本実施例15では、ステップU51~U5Aが充電ステップに相当する。
実施例16は、実施例15と比較して、放電期間の長さのみが異なり、その他については同様である。具体的には、本実施例16では、各放電期間の長さを1.0秒にして、リチウムイオン二次電池100の充電(ステップU51~U5A)を行う。
実施例17では、実施例15と異なり、非充電期間を充電休止期間と放電期間とにしている。すなわち、各々の非充電期間において、充電休止と放電を行う。
具体的には、電池コントローラ30は、リチウムイオン二次電池100の蓄電量が第2規定値に達するまでの充電期間を、3つの分割充電期間(第1~第3分割充電期間)と、各々の分割充電期間の間の非充電期間とに分割する。そして、各分割充電期間に充電を行うと共に、各非充電期間に充電休止と放電を行う。すなわち、「充電、休止、放電、充電、休止、放電、充電」と行って、蓄電量を第2規定値にまで回復させる。
まず、図15に示すように、実施例15と同様に、ステップS1~S4の処理を行う。次いで、ステップV5の充電ルーチンに進む。具体的には、図18に示すように、ステップV51において、組電池10を構成するリチウムイオン二次電池100の充電を開始する。具体的には、エンジン3の稼働により発電機9が駆動している状態で、この発電機9により発電された電力を、組電池10を構成するリチウムイオン二次電池100に供給する。本実施例17でも、電流の大きさを3C(15A)で一定として、リチウムイオン二次電池100に供給する。
その後、ステップV52において、第1分割充電期間が経過した(Yes)と判定されると、ステップV53に進み、リチウムイオン二次電池100の充電を休止する。
ステップV54において、充電休止期間が経過していない(No)と判定された場合には、充電休止期間が経過するまで、この処理を繰り返す。その後、ステップV54において、充電休止期間が経過した(Yes)と判定されると、ステップV55に進み、リチウムイオン二次電池100の放電を開始する。本実施例17でも、7.5Aの定電流で放電を行う。
ステップV56において、放電期間が経過していない(No)と判定された場合には、放電期間が経過するまで、この処理を繰り返す。その後、ステップV56において、放電期間が経過した(Yes)と判定されると、ステップV57に進み、リチウムイオン二次電池100の充電を再開する。
その後、ステップV58において、第2分割充電期間が経過した(Yes)と判定されると、ステップV59に進み、リチウムイオン二次電池100の充電を休止する。
ステップV5Aにおいて、充電休止期間が経過していない(No)と判定された場合には、充電休止期間が経過するまで、この処理を繰り返す。その後、ステップV5Aにおいて、充電休止期間が経過した(Yes)と判定されると、ステップV5Bに進み、リチウムイオン二次電池100の放電を開始する。ここでも、7.5Aの定電流で放電を行う。
ステップV5Cにおいて、放電期間が経過していない(No)と判定された場合には、放電期間が経過するまで、この処理を繰り返す。その後、ステップV5Cにおいて、放電期間が経過した(Yes)と判定されると、ステップV5Dに進み、リチウムイオン二次電池100の充電を再開する。
なお、本実施例17では、ステップV51~V5Eが充電ステップに相当する。
リチウムイオン二次電池100について、第1規定値(SOC30%に相当する蓄電量)から第2規定値(SOC60%に相当する蓄電量)にまで充電し、その後、第1規定値にまで放電させる充放電サイクルを1サイクルとして、サイクル試験を行った。このサイクル試験について、以下に詳細に説明する。
次に、変形例1にかかるリチウムイオン二次電池の充電方法について説明する。
実施例1では、ステップS6において、第1分割充電期間が経過したか否かを判定するようにした(図7参照)。具体的には、第1分割充電期間KC1の長さtcを67.5秒間に設定し、ステップS5において充電を開始してから67.5秒が経過したか否かを判定するようにした。
具体的には、図7、図14、図15のステップS1において、リチウムイオン二次電池100の端子間電圧Vが、第1規定値(SOC30%に相当する蓄電量に対応する端子間電圧値V1)にまで低下しているか否かを判定するようにしても良い。詳細には、予め取得した、リチウムイオン二次電池100の蓄電量の値と端子間電圧Vの値との対応関係を示す「蓄電量-電圧相関マップ」に基づいて、電池コントローラ30のROM31に、SOC30%の蓄電状態のときの端子間電圧値V1を、第1規定値として記憶させておく。これにより、電圧検知手段40において端子間電圧値V1が検知されると、電池コントローラ30により、リチウムイオン二次電池100の端子間電圧Vが、第1規定値にまで低下していると判定することができる。
これと同様にして、図7,図14のステップSA及び図16,図18のステップU5A,V5Eにおいて、リチウムイオン二次電池100の端子間電圧Vが、第2規定値(SOC60%の蓄電状態のときの端子間電圧値V2)に達したか否かを判定するようにしても良い。また、図14のステップT6において、リチウムイオン二次電池100の端子間電圧Vが、分割規定値(SOC45%の蓄電状態のときの端子間電圧値V3)に達したか否かを判定するようにしても良い。
まず、参考例1にかかるサイクル試験について説明する。リチウムイオン二次電池100について、0℃の温度環境下において、80A(16C)の定電流で、終止電圧の4.3Vに達するまで充電した後、4.3Vの定電圧で充電することで、SOC100%程度にまで充電する。その後、180秒間休止する。次いで、1Aの定電流で、終止電圧の3.726Vに達するまで放電した後、3.726Vの定電圧で放電することで、SOC60%程度に調整する。その後、420秒間休止する。この充放電サイクルを1サイクルとして、3092サイクル行った。
この結果より、本発明の充電方法において、非充電期間に、リチウムイオン二次電池100を放電させることで、負極表面における金属Liの析出を抑制して、電気容量の低下を抑制することができるといえる。
Claims (12)
- 駆動用電源としてハイブリッド自動車に搭載されたリチウムイオン二次電池の充電方法であって、
上記リチウムイオン二次電池の蓄電量に対応する物理量の値が、第1規定値にまで低下しているか否かを判定するステップと、
上記ハイブリッド自動車が走行停止状態であるか否かを判定するステップと、
上記リチウムイオン二次電池の蓄電量に対応する物理量の値が上記第1規定値にまで低下していると判定され、且つ、上記ハイブリッド自動車が走行停止状態であると判定された場合に、上記ハイブリッド自動車の走行停止中に、上記リチウムイオン二次電池の蓄電量に対応する物理量の値が第2規定値に達するまで、上記リチウムイオン二次電池を充電する充電ステップであって、
上記充電を行う期間を、2以上の分割充電期間と、各々の上記分割充電期間の間の非充電期間とに分割し、上記分割充電期間に充電を行うと共に、上記非充電期間に充電休止及び放電の少なくともいずれかを行い、且つ、
各々の上記分割充電期間の長さをいずれも40秒以上とする
充電ステップと、を備える
リチウムイオン二次電池の充電方法。 - 請求の範囲第1項に記載のリチウムイオン二次電池の充電方法であって、
前記非充電期間を、前記リチウムイオン二次電池の充電を休止する充電休止期間とし、
各々の前記分割充電期間の長さtcと、その直後の上記充電休止期間の長さtrとの比tr/tcを、0.14以上0.9以下とする
リチウムイオン二次電池の充電方法。 - 請求の範囲第1項に記載のリチウムイオン二次電池の充電方法であって、
前記非充電期間を、前記リチウムイオン二次電池の放電を行う放電期間とする
リチウムイオン二次電池の充電方法。 - 請求の範囲第1項に記載のリチウムイオン二次電池の充電方法であって、
各々の前記非充電期間を、前記リチウムイオン二次電池の充電を休止する充電休止期間と上記リチウムイオン二次電池の放電を行う放電期間とにする
リチウムイオン二次電池の充電方法。 - 請求の範囲第1項~第4項のいずれか一項に記載のリチウムイオン二次電池の充電方法であって、
前記ハイブリッド自動車に搭載されているエンジンが稼働状態であるか否かを判定するステップと、
上記エンジンが稼働していないと判定された場合、上記エンジンの稼働を指示するステップと、を備え、
前記充電ステップは、
上記エンジンの稼働により上記ハイブリッド自動車に搭載されている発電機が駆動している状態で、この発電機により発電された電力を前記リチウムイオン二次電池に供給して上記リチウムイオン二次電池を充電する
リチウムイオン二次電池の充電方法。 - 請求の範囲第1項~第5項のいずれか一項に記載のリチウムイオン二次電池の充電方法であって、
前記リチウムイオン二次電池に含まれる正極活物質が理論的に最大限蓄積できる理論電気容量を1時間で充電することができる電流値を1Cとしたとき、
前記充電ステップは、2C以上の大きさの電流で、上記リチウムイオン二次電池を充電する
リチウムイオン二次電池の充電方法。 - ハイブリッド自動車であって、
駆動用電源として上記ハイブリッド自動車に搭載されたリチウムイオン二次電池と、
上記リチウムイオン二次電池の蓄電量に対応する物理量の値が、第1規定値にまで低下しているか否かを判定する第1判定手段と、
上記ハイブリッド自動車が走行停止状態であるか否かを判定する停止状態判定手段と、
上記リチウムイオン二次電池の蓄電量に対応する物理量の値が上記第1規定値にまで低下していると判定され、且つ、上記ハイブリッド自動車が走行停止状態であると判定された場合に、上記ハイブリッド自動車の走行停止中に、上記リチウムイオン二次電池の蓄電量に対応する物理量の値が第2規定値に達するまで、上記リチウムイオン二次電池の充電制御を行う充電制御手段であって、
上記充電を行う期間を、2以上の分割充電期間と、各々の上記分割充電期間の間の非充電期間とに分割し、上記分割充電期間に充電を行うと共に、上記非充電期間に充電休止及び放電の少なくともいずれかを行い、且つ、
各々の上記分割充電期間の長さをいずれも40秒以上とする
充電制御手段と、を備える
ハイブリッド自動車。 - 請求の範囲第7項に記載のハイブリッド自動車であって、
前記充電制御手段は、
前記非充電期間を、前記リチウムイオン二次電池の充電を休止する充電休止期間とし、
各々の前記分割充電期間の長さtcと、その直後の上記充電休止期間の長さtrとの比tr/tcを、0.14以上0.9以下として、上記リチウムイオン二次電池の充電制御を行う
ハイブリッド自動車。 - 請求の範囲第7項に記載のハイブリッド自動車であって、
前記充電制御手段は、
前記非充電期間を、前記リチウムイオン二次電池の放電を行う放電期間としてなる
ハイブリッド自動車。 - 請求の範囲第7項に記載のハイブリッド自動車であって、
前記充電制御手段は、
各々の前記非充電期間を、前記リチウムイオン二次電池の充電を休止する充電休止期間と上記リチウムイオン二次電池の放電を行う放電期間とにしてなる
ハイブリッド自動車。 - 請求の範囲第7項~第10項のいずれか一項に記載のハイブリッド自動車であって、
前記ハイブリッド自動車に搭載されているエンジンが稼働しているか否かを判定するエンジン稼働判定手段と、
上記エンジンが稼働していないと判定された場合、上記エンジンの稼働を指示するエンジン稼働指示手段と、を備え、
前記充電制御手段は、
上記エンジンの稼働により上記ハイブリッド自動車に搭載されている発電機が駆動している状態で、この発電機により発電された電力を前記リチウムイオン二次電池に供給して上記リチウムイオン二次電池を充電する制御を行う
ハイブリッド自動車。 - 請求の範囲第7項~第11項のいずれか一項に記載のハイブリッド自動車であって、
前記リチウムイオン二次電池に含まれる正極活物質が理論的に最大限蓄積できる理論電気容量を1時間で充電することができる電流値を1Cとしたとき、
前記充電制御手段は、2C以上の大きさの電流で、上記リチウムイオン二次電池を充電する制御を行う
ハイブリッド自動車。
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- 2009-01-09 CN CN2009801021534A patent/CN101909929B/zh not_active Expired - Fee Related
- 2009-01-09 RU RU2010127442/11A patent/RU2471276C2/ru active
- 2009-01-09 BR BRPI0907218-7A patent/BRPI0907218B1/pt active IP Right Grant
- 2009-01-09 US US12/740,434 patent/US8310198B2/en active Active
- 2009-01-09 CA CA2701160A patent/CA2701160C/en active Active
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CN103155347A (zh) * | 2010-12-13 | 2013-06-12 | 三洋电机株式会社 | 充电设备、电力存储设备以及电源设备 |
US9252622B2 (en) | 2010-12-13 | 2016-02-02 | Panasonic Intellectual Property Management Co., Ltd. | Charging apparatus, power storage apparatus, and power source apparatus |
JP2018055804A (ja) * | 2016-09-26 | 2018-04-05 | トヨタ自動車株式会社 | リチウムイオン二次電池の回復処理方法 |
WO2018088260A1 (ja) * | 2016-11-10 | 2018-05-17 | Necエナジーデバイス株式会社 | 制御装置、制御方法、及びプログラム |
CN110024257A (zh) * | 2016-11-10 | 2019-07-16 | 远景Aesc能源元器件有限公司 | 控制装置、控制方法和程序 |
JPWO2018088260A1 (ja) * | 2016-11-10 | 2019-09-26 | 株式会社エンビジョンAescエナジーデバイス | 制御装置、制御方法、及びプログラム |
US11245137B2 (en) | 2016-11-10 | 2022-02-08 | Envision Aesc Japan Ltd. | Control apparatus, control method, and program |
CN110024257B (zh) * | 2016-11-10 | 2022-11-25 | 远景Aesc日本有限公司 | 控制装置、控制方法和计算机可读存储介质 |
Also Published As
Publication number | Publication date |
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KR20100087383A (ko) | 2010-08-04 |
EP2230124B9 (en) | 2016-05-11 |
RU2010127442A (ru) | 2012-02-27 |
US8310198B2 (en) | 2012-11-13 |
EP2230124A1 (en) | 2010-09-22 |
JPWO2009090913A1 (ja) | 2011-05-26 |
CA2701160C (en) | 2013-10-01 |
US20100259219A1 (en) | 2010-10-14 |
KR101160755B1 (ko) | 2012-06-28 |
CA2701160A1 (en) | 2009-07-23 |
CN101909929A (zh) | 2010-12-08 |
RU2471276C2 (ru) | 2012-12-27 |
BRPI0907218B1 (pt) | 2022-08-23 |
BRPI0907218A2 (pt) | 2022-03-29 |
EP2230124A4 (en) | 2014-08-06 |
EP2230124B1 (en) | 2015-10-07 |
BRPI0907218A8 (pt) | 2022-06-28 |
CN101909929B (zh) | 2012-09-05 |
JP4572998B2 (ja) | 2010-11-04 |
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