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WO2018181620A1 - Dispositif d'estimation de quantité d'électricité stockée, module de stockage d'électricité, procédé d'estimation de quantité d'électricité stockée et programme d'ordinateur - Google Patents

Dispositif d'estimation de quantité d'électricité stockée, module de stockage d'électricité, procédé d'estimation de quantité d'électricité stockée et programme d'ordinateur Download PDF

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Publication number
WO2018181620A1
WO2018181620A1 PCT/JP2018/013053 JP2018013053W WO2018181620A1 WO 2018181620 A1 WO2018181620 A1 WO 2018181620A1 JP 2018013053 W JP2018013053 W JP 2018013053W WO 2018181620 A1 WO2018181620 A1 WO 2018181620A1
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Prior art keywords
voltage value
storage amount
soc
amount
discharge
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PCT/JP2018/013053
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English (en)
Japanese (ja)
Inventor
南 鵜久森
祐一 池田
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株式会社Ｇｓユアサ
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Application filed by 株式会社Ｇｓユアサ filed Critical 株式会社Ｇｓユアサ
Priority to US16/498,280 priority Critical patent/US11181584B2/en
Priority to EP18774740.7A priority patent/EP3605122B1/fr
Priority to CN201880022409.XA priority patent/CN110462413B/zh
Priority claimed from JP2018062290A external-priority patent/JP6406468B1/ja
Publication of WO2018181620A1 publication Critical patent/WO2018181620A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/382—Arrangements for monitoring battery or accumulator variables, e.g. SoC
    • G01R31/3842—Arrangements for monitoring battery or accumulator variables, e.g. SoC combining voltage and current measurements
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a storage amount estimation device that estimates a storage amount such as SOC (State Of Charge) of a storage element, a storage module including the storage amount estimation device, a storage amount estimation method, and a computer program.
  • SOC State Of Charge
  • High capacity is required for secondary batteries for vehicles used in electric cars, hybrid cars, etc., and for industrial secondary batteries used in power storage devices, solar power generation systems, and the like.
  • Various examinations and improvements have been made so far, and it is difficult to realize a higher capacity only by improving the electrode structure and the like. For this reason, development of a positive electrode material having a higher capacity than the current material is underway.
  • lithium transition metal composite oxides having an ⁇ -NaFeO 2 type crystal structure have been studied as positive electrode active materials for non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries, and non-aqueous electrolyte secondary batteries using LiCoO 2 have been studied. Secondary batteries have been widely used.
  • the discharge capacity of LiCoO 2 was about 120 to 160 mAh / g.
  • the lithium transition metal composite oxide is represented by LiMeO 2 (Me is a transition metal)
  • Mn is included as Me, if the molar ratio Mn / Me in Me exceeds 0.5, the structure changes to a spinel type when charged and the crystal structure cannot be maintained. Cycle performance is extremely inferior.
  • LiMeO 2 type active materials in which the molar ratio Mn / Me in Me is 0.5 or less and the molar ratio Li / Me to Me is approximately 1 have been proposed and put to practical use.
  • the positive electrode active material containing LiNi 1/2 Mn 1/2 O 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 which are lithium transition metal composite oxides has a discharge capacity of 150 to 180 mAh / g. Have.
  • Lithium transition metal composite oxide in which Mn molar ratio Mn / Me in Me exceeds 0.5 and Li composition ratio Li / Me is greater than 1 with respect to the ratio of transition metal (Me) to LiMeO 2 type active material
  • Mn molar ratio Mn / Me in Me exceeds 0.5
  • Li composition ratio Li / Me is greater than 1 with respect to the ratio of transition metal (Me) to LiMeO 2 type active material
  • Li 2 MnO 3 -based active material As the above-described high-capacity positive electrode material, a lithium-excess type Li 2 MnO 3 -based active material has been studied. This material has a property of hysteresis in which a voltage value and electrochemical characteristics with respect to the same SOC (State Of Charge) change depending on a charge history and a discharge history.
  • SOC State Of Charge
  • the OCV method (refer to voltage) for determining the SOC based on the correlation (SOC-OCV curve) in which the OCV (Open Circuit Voltage) of the secondary battery and the SOC correspond one-to-one.
  • a current integration method in which the SOC is determined by integrating the charge / discharge current values of the secondary battery.
  • SOC i SOC i-1 + I i ⁇ ⁇ t i / Q ⁇ 100 (1)
  • SOC i This SOC SOC i-1 : Previous SOC I: current value ⁇ t: time interval Q: battery capacity (available capacity)
  • the relationship between SOC and OCV in the discharging process is stored as discharging OCV information for each switching SOC, which is the SOC when switching from charging to discharging.
  • the secondary battery control device is configured to calculate the SOC in the discharging process of the secondary battery based on the switching SOC at the time of actually switching from charging to discharging and the discharging OCV information.
  • an SOC-OCV curve at the time of discharge is selected from the voltage value reached by charging, and the SOC is estimated based on the SOC-OCV curve and the current voltage value.
  • the SOC cannot be estimated based on the voltage value of the charging process.
  • the present invention relates to a storage amount estimation device capable of estimating a storage amount of a storage element including an active material whose storage amount-voltage value characteristic exhibits hysteresis, a storage module including the storage amount estimation device, a storage amount estimation method, and a computer program.
  • the purpose is to provide.
  • the amount of power storage means SOC, the amount of electric power that can be discharged, and the like.
  • the power storage amount estimation device generates two or more electrochemical reactions according to the charge / discharge transition, and the stored power-voltage value charge according to the charge transition shown when one electrochemical reaction occurs.
  • an electricity storage element including an active material in at least one of a positive electrode and a negative electrode, wherein the hysteresis between the characteristics and the amount of stored electricity according to the transition of discharge-voltage value discharge characteristics is smaller than the hysteresis when other electrochemical reaction occurs
  • An estimation unit is provided that estimates the amount of electricity stored using the voltage value characteristics.
  • “when one electrochemical reaction occurs” includes “when an electrochemical reaction occurs as a group simultaneously”. “When another electrochemical reaction occurs” includes “when an electrochemical reaction occurs as a group simultaneously”.
  • Charge amount-voltage value charge characteristics and charge amount-voltage value discharge when charging from a fully discharged state to a fully charged state, or discharging from a fully charged state to a fully discharged state (hereinafter referred to as full charge or full discharge) Characteristics may be acquired.
  • the difference between the storage amounts of both characteristics at the same voltage value ( ⁇ storage amount) corresponds to another electrochemical reaction.
  • One electrochemical reaction and the other electrochemical reaction occur substantially independently. That is, the reaction amount of other electrochemical reaction corresponds to the ⁇ storage amount, and hardly affects one electrochemical reaction.
  • the voltage reference storage amount-voltage value characteristics are changed by moving the storage amount-voltage value discharge characteristics toward the storage amount-voltage value charging characteristics. You may get it. That is, the voltage reference storage amount-voltage value characteristic starting from each voltage value moves the same storage amount-voltage value discharge characteristic toward the storage amount-voltage value charge characteristic based on one electrochemical reaction, It has a shape cut out with the voltage value of each starting point as the upper end.
  • the storage amount of the storage element having an active material having a high capacity and having a storage amount-voltage value characteristic exhibiting hysteresis Only the storage amount-voltage value discharge characteristics and the storage amount-voltage value charging characteristics are actually measured, and the amount of work is small.
  • voltage reference storage amount to be positioned between adjacent voltage reference storage amount-voltage value characteristics-voltage value characteristics are obtained by interpolation and compensated, voltage reference storage amount corresponding to each reached voltage value- Since the voltage value characteristic is directly generated from the actually measured storage amount-voltage value discharge characteristic, the accuracy of the storage amount estimation is improved.
  • the storage amount-voltage value discharge characteristic and the storage amount-voltage value charge characteristic are actually measured.
  • the amount of work is small. Since the voltage value can be used, the amount of electricity stored is not limited to the SOC, and the amount of current energy stored in the electricity storage element such as the amount of power can be estimated. Based on the charge / discharge curve, the dischargeable energy up to SOC 0% and the charge energy required up to SOC 100% can be predicted.
  • mold active material It is a graph which shows transition of the K absorption edge energy of Ni of the Li excess type active material computed by X-ray absorption spectroscopy measurement (XAFS measurement) with respect to the electric quantity. It is a graph which shows transition of the K absorption edge energy of Ni at the time of charging / discharging. It is a graph which shows the result of having calculated
  • FIG. 7 is a graph showing a difference between when the SOC is estimated by referring to the voltage of the present embodiment and when the SOC is estimated by current integration when charging / discharging shown in FIG. It is explanatory drawing for demonstrating the principle of SOC estimation of this embodiment.
  • FIG. 5 is an SOC-OCV curve obtained by actual measurement when the SOC is 40 to 60%.
  • FIG. 6 is a reference SOC-OCV curve obtained by the method of the present embodiment when the SOC is 40 to 60%.
  • 11 is a graph showing a difference between the SOC-OCV curve a in FIG. 9 and the reference SOC-OCV curve b in FIG.
  • It is a perspective view which shows an example of an electrical storage module. It is a perspective view which shows the other example (battery module) of an electrical storage module. It is a disassembled perspective view of the battery module of FIG. It is a block diagram of a battery module.
  • It is a flowchart which shows the procedure of the SOC estimation process by CPU. It is a flowchart which shows the procedure of the SOC estimation process by CPU. It is a flowchart which shows the procedure of the SOC estimation process by CPU. It is a flowchart which shows the procedure of the SOC estimation process by CPU.
  • the electrode body of the power storage device includes an active material having a stored power-voltage value characteristic having hysteresis.
  • the active material of the electricity storage element is a Li-rich LiMeO 2 —Li 2 MnO 3 solid solution containing Ni and the amount of electricity stored is SOC will be described as an example.
  • FIG. 1 is a graph showing the results of determining the relationship between the amount of electricity and the charge / discharge voltage value for this Li-excess type active material using a lithium cell of the counter electrode Li.
  • the horizontal axis represents the amount of electricity (mAh / g), and the vertical axis represents the charge / discharge voltage value E (VvsLi / Li + : Li / Li + potential difference based on the equilibrium potential).
  • the amount of electricity corresponds to the SOC.
  • the voltage value differs between an increase (charge) and a decrease (discharge) of the SOC. That is, the voltage values for the same SOC are different and have hysteresis. In the case of this active material, the potential difference with respect to the same SOC is smaller in the high SOC region than in the low SOC region, and the hysteresis is small.
  • FIG. 2 is a graph showing the transition of the K absorption edge energy of Ni of the Li-rich active material calculated by X-ray absorption spectroscopy measurement (XAFS measurement) with respect to the amount of electricity.
  • the horizontal axis represents the amount of electricity (mAh / g), and the vertical axis represents the K absorption edge energy E 0 (eV) of Ni.
  • FIG. 3 is a graph showing the transition of the K absorption edge energy of Ni during charging and discharging.
  • the horizontal axis represents the charge / discharge voltage value E (VvsLi / Li + )
  • the vertical axis represents the K absorption edge energy E 0 (eV) of Ni.
  • the K absorption edge energy transition of Ni in the charge reaction does not coincide with the energy transition of the discharge reaction.
  • the energy transition of the discharge reaction does not coincide with the energy transition of the charge reaction. That is, it can be seen that a redox reaction other than Ni that has hysteresis occurs mainly (this reaction is A reaction).
  • the reaction A is an oxidation reaction in the high SOC region and a reduction reaction in the low SOC region.
  • the K absorption edge energy of Ni in the charge reaction and the discharge reaction changes substantially linearly with respect to the SOC.
  • the K absorption edge energy of Ni is substantially the same between charge and discharge.
  • the valence of Ni is equal, and in this voltage range, the valence change of Ni corresponds to a voltage value of approximately 1: 1, and Ni is reversible. It is thought that it is reacting. That is, in the SOC region, a redox reaction with a small hysteresis indicated by the SOC-OCP characteristic is mainly generated (this reaction is referred to as B reaction).
  • OCP means an open circuit potential.
  • the reaction amount of B is larger than the reaction amount of A, and as a result, the hysteresis is smaller than that in the low SOC region.
  • the lower voltage value (lower limit voltage value) in the region where the reaction of B mainly occurs is obtained by experiments.
  • the presence or absence of hysteresis is substantially switched.
  • the oxidation amount and reduction amount of the reaction of B are considered to be small.
  • the SOC is estimated by voltage reference based on the reached voltage value.
  • the description is given focusing only on the oxidation-reduction reaction of Ni, but the reaction of B is not limited to the oxidation-reduction reaction of Ni.
  • the reaction B is a reaction in which the hysteresis of the storage amount-voltage value characteristic is small among one or a group of reactions caused by the active material according to the transition of charge / discharge.
  • FIG. 4 is a graph showing the results of determining the relationship between the amount of electricity and the charge / discharge voltage value using a lithium cell of the counter electrode Li for this power storage element.
  • the horizontal axis represents the amount of electricity (mAh / g), and the vertical axis represents the charge / discharge voltage value (VvsLi / Li + : Li / Li + potential difference based on the equilibrium potential).
  • the amount of electricity corresponds to the SOC.
  • the voltage value differs between the charge curve and the discharge curve. That is, the voltage values for the same SOC are different and have hysteresis. In the case of this active material, the potential difference with respect to the same SOC is smaller in the high SOC region than in the low SOC region, and the hysteresis is small.
  • FIG. 5 is a charge / discharge curve in a case where a region having a large hysteresis and a region having a small hysteresis appear alternately as the SOC (or voltage value) increases.
  • the horizontal axis represents SOC (%), and the vertical axis represents voltage value (V).
  • the hysteresis is smaller than in the region (1) where the voltage value is a or less.
  • a reaction of C having a large hysteresis and a reaction of D having a small hysteresis occur. Since the reaction amount of D is large in the region (2), the hysteresis is smaller than that in the region (1) as a result.
  • the hysteresis is smaller than in the region (3) where the voltage value is b to c.
  • the lower limit voltage value a of the region (2) and the lower limit voltage value c of the region (4) are obtained by experiments. When it is determined that the charged state or the discharged state is in the region (2) corresponding to the voltage region above the lower limit voltage value a based on the rise and fall of the voltage value, and the region corresponding to the voltage region above the lower limit voltage value c When it determines with it being in (4), each SOC is estimated by voltage reference based on the ultimate voltage value mentioned later.
  • the voltage value region is not limited to the case where the voltage value region is divided into two or four regions as described above.
  • the SOC is referred by voltage reference. Is estimated.
  • the lower limit voltage value When OCV can be measured as the lower limit voltage value, the lower limit voltage value may be constant. When measuring the CCV as the lower limit voltage value, it may be updated, for example, by lowering the lower limit voltage value in accordance with the degree of deterioration associated with the use of the storage element.
  • causes of deterioration of the power storage element include an increase in internal resistance and an increase in deviation in capacity balance.
  • the difference in capacity balance is, for example, that a difference occurs between the amount of side reactions other than the charge / discharge reaction at the positive electrode and the amount of side reactions other than the charge / discharge reaction at the negative electrode. Is not charged and the positive and negative electrodes have different capacities in which charge ions can enter and leave the electrode reversibly.
  • a plurality of voltage reference SOC-OCV curves (hereinafter referred to as reference SOC-OCV curves) from the lower limit voltage value to a plurality of ultimate voltage values are stored in the memory table of the storage amount estimation device.
  • reference SOC-OCV curves For example, the SOC-OCV curve a from the lower limit voltage value E0 V to the ultimate voltage value E1 V, the SOC-OCV curve b from the lower limit voltage value E0 V to the ultimate voltage value E2 V, and the lower limit voltage value E0 V to the ultimate voltage value E3 V SOC-OCV curves c up to are stored.
  • SOC-OCV curves a, b, and c are referred to in a comparative test described later, but are not shown.
  • SOC-OCV curves corresponding to all ultimate voltage values are stored continuously, not discretely. Instead of storing continuously, SOC-OCV curves may be prepared discretely, and a curve to be positioned between adjacent SOC-OCV curves may be obtained by interpolation and compensated.
  • the reference SOC-OCV curve is obtained as follows. A discharge OCV curve and a charge OCV curve are obtained for each SOC (%) where the SOC is 40% to 100% when each SOC (%) is changed from 40% to 100%.
  • the discharge OCV curve can be obtained, for example, by passing a small current in the discharge direction and measuring the voltage value at that time. Alternatively, it is also possible to measure a voltage value in which the voltage value is stabilized by discharging from the charged state to each SOC and stopping.
  • the charging OCV can be obtained by performing the above measurement in the charging direction.
  • an OCV curve obtained by averaging the discharge OCV curve and the charge OCV curve obtained by averaging the discharge OCV curve and the charge OCV curve.
  • a discharge OCV curve and a charge OCV curve, or those obtained by correcting them may be used. Note that the discharge OCP curve and the charge OCP curve may be obtained first, and then corrected to the reference SOC-OCV curve of the storage element.
  • FIG. 6 is a graph showing the transition of the voltage value with respect to time during charging and discharging.
  • the horizontal axis represents time (seconds), and the vertical axis represents the charge / discharge voltage value (VvsLi / Li + ).
  • VvsLi / Li + the charge / discharge voltage value
  • E3V is stored as the first reached voltage value.
  • the reached voltage value is updated when it exceeds E3 ⁇ ⁇ V in the second charge.
  • the SOC-OCV curve c is used until E3EV is reached in the first discharge and the second charge.
  • Another SOC-OCV curve stored in the table is used during the second charge from E3 V to E1 ⁇ V.
  • the SOC-OCV curve a is used between E1 V of the second discharge and the lower limit voltage value E0 V.
  • FIG. 7 shows the difference between when the SOC is estimated by referring to the voltage of the present embodiment and when the SOC is estimated by conventional current integration when the charge and discharge shown in FIG. It is a graph which shows.
  • the horizontal axis represents time (seconds), the left vertical axis represents SOC (%), and the right vertical axis represents the difference (%).
  • the estimation of the SOC by current integration as a control confirms the discharge capacity in advance and uses a highly accurate ammeter, so that the discharge capacity of Q and the current value of I in the formula (1) are accurate. It is. It is thought that it approximates the true value.
  • d is the transition of the SOC obtained by current integration
  • e is the transition of the SOC obtained by voltage reference using the SOC-OCV curves c and a
  • f is the difference.
  • the difference was obtained by (SOC calculated by voltage reference) ⁇ (SOC calculated by current integration).
  • FIG. 7 shows that the difference is less than about ⁇ 4% and is small. From the above, it was confirmed that the accuracy of SOC estimation by the reference SOC-OCV curve is good.
  • a discharge SOC-OCV curve when fully discharged and a charge SOC-OCV curve when fully charged are prepared.
  • the difference between the SOC at a certain voltage value on the discharge SOC-OCV curve and the SOC at the same voltage value on the charge SOC-OCV curve is defined as ⁇ SOC.
  • the reaction of A and the reaction of B occur substantially independently.
  • the reaction amount of A corresponds to ⁇ SOC and does not affect the reaction of B. Therefore, it was considered that the reference SOC-OCV curve can be easily obtained by correcting with ⁇ SOC based on the discharge SOC-OCV curve of the reaction B.
  • the reference SOC-OCV curve starting from each reached voltage value is corrected by moving the same discharge SOC-OCV curve toward the charge SOC-OCV curve based on the reaction of the same B, and the reaching voltage at each starting point is corrected. It has a shape that is cut with the value as the upper end.
  • FIG. 8 is an explanatory diagram for explaining this principle.
  • the horizontal axis represents SOC [%], and the vertical axis represents the charge / discharge voltage value E (VvsLi / Li + ).
  • (1) is a full discharge SOC-OCV curve
  • (2) is a full charge SOC-OCV curve.
  • the difference between the SOC at a certain reached voltage value on the discharge SOC-OCV curve (1) and the SOC at the same reached voltage value on the charge SOC-OCV curve (2) is ⁇ SOC.
  • the SOC-OCV curve (3) is obtained by sliding the discharge SOC-OCV curve (1) toward the charge SOC-OCV curve (2) side in parallel with the horizontal axis by this ⁇ SOC.
  • the SOC-OCV curve (3) in the range from the lower limit voltage value to the ultimate voltage value is taken as the reference SOC-OCV curve.
  • the SOC corresponding to the acquired voltage value is read using the reference SOC-OCV curve.
  • FIG. 9 is an SOC-OCV curve obtained by actual measurement when the SOC is 40 to 60%.
  • the horizontal axis represents SOC (%), and the vertical axis represents the charge / discharge voltage value E (VvsLi / Li + : Li / Li + potential difference based on the equilibrium potential).
  • FIG. 10 is a reference SOC-OCV curve obtained by the above-described method when the SOC is 40 to 60%.
  • the horizontal axis represents SOC (%), and the vertical axis represents the charge / discharge voltage value E (VvsLi / Li + : Li / Li + potential difference based on the equilibrium potential).
  • FIG. 11 is a graph showing a difference between the SOC-OCV curve a in FIG.
  • the horizontal axis is SOC (%)
  • the left vertical axis is the charge / discharge voltage value E (VvsLi / Li + : potential difference based on Li / Li + equilibrium potential)
  • the right vertical axis is the difference (V). .
  • the shape of the reference SOC-OCV curve from the lower limit voltage value to the reached upper limit voltage matches the shape of the discharge curve at the time of full discharge at the same voltage.
  • the reference SOC-OCV curve corresponding to each ultimate voltage value can be easily obtained from the lower limit voltage value. Only the full discharge SOC-OCV curve and the full charge SOC-OCV curve are actually measured, and the amount of work to be examined in advance is significantly reduced. Compared to the case where a curve to be positioned between adjacent SOC-OCV curves is obtained by interpolation calculation and compensated, the reference SOC-OCV curve corresponding to each ultimate voltage value is measured as a full charge / discharge SOC-OCV curve. Therefore, the accuracy of SOC estimation is improved.
  • a reference SOC-OCV curve is generated according to the deterioration of the storage element. In this case, only the full charge / discharge SOC-OCV curve is actually measured, and the amount of work during the use period of the power storage element is significantly reduced.
  • the SOC is preferably estimated from the current electrochemical behavior and usage history.
  • FIG. 12 shows an example of a power storage module.
  • the power storage module 50 includes a plurality of power storage elements 200, a monitoring device 100, and a storage case 300 that stores them.
  • the power storage module 50 may be used as a power source for an electric vehicle (EV) or a plug-in hybrid electric vehicle (PHEV).
  • the power storage element 200 is not limited to a square cell, and may be a cylindrical cell or a pouch cell.
  • the monitoring device 100 may be a circuit board arranged to face the plurality of power storage elements 200. Monitoring device 100 monitors the state of power storage element 200.
  • the monitoring device 100 may be a storage amount estimation device. Alternatively, a computer or server that is wired or wirelessly connected to the monitoring device 100 may execute the storage amount estimation method based on information output from the monitoring device 100.
  • FIG. 13 shows another example of the power storage module.
  • the power storage module (hereinafter referred to as a battery module) 1 may be a 12-volt power source or a 48-volt power source that is suitably mounted on an engine vehicle.
  • 13 is a perspective view of the battery module 1 for 12V power supply
  • FIG. 14 is an exploded perspective view of the battery module 1
  • FIG. 15 is a block diagram of the battery module 1.
  • the battery module 1 has a rectangular parallelepiped case 2.
  • the case 2 houses a plurality of lithium ion secondary batteries (hereinafter referred to as batteries) 3, a plurality of bus bars 4, a BMU (Battery Management Unit) 6, and a current sensor 7.
  • batteries hereinafter referred to as batteries
  • BMU Battery Management Unit
  • the battery 3 includes a rectangular parallelepiped case 31 and a pair of terminals 32 and 32 provided on one side of the case 31 and having different polarities.
  • the case 31 accommodates an electrode body 33 in which a positive electrode plate, a separator, and a negative electrode plate are stacked.
  • At least one of the positive electrode active material included in the positive electrode plate of the electrode body 33 and the negative electrode active material included in the negative electrode plate causes two or more electrochemical reactions depending on the transition of charge / discharge.
  • the hysteresis of the charged amount-voltage value characteristic shown when one electrochemical reaction occurs is smaller than the hysteresis when the other electrochemical reaction occurs.
  • LiMeO 2 -Li 2 MnO 3 solid solution described above, Li 2 O-LiMeO 2 solid solution, Li 3 NbO 4 -LiMeO 2 solid solution, Li 4 WO 5 -LiMeO 2 solid solution, Li 4 TeO 5 -LiMeO 2 solid solution, Li 3 SbO 4 -LiFeO 2 solid solution, Li 2 RuO 3 -LiMeO 2 solid solution, and a Li-excess active material such as Li 2 RuO 3 -Li 2 MeO 3 solid solution.
  • Examples of the negative electrode active material include metals or alloys such as hard carbon, Si, Sn, Cd, Zn, Al, Bi, Pb, Ge, and Ag, or chalcogenides containing these.
  • An example of the chalcogenide is SiO.
  • the technology of the present invention is applicable as long as at least one of these positive electrode active materials and negative electrode active materials is included.
  • Case 2 is made of synthetic resin.
  • the case 2 includes a case main body 21, a lid portion 22 that closes the opening of the case main body 21, a BMU housing portion 23 provided on the outer surface of the lid portion 22, a cover 24 that covers the BMU housing portion 23, and an inner lid 25 and a partition plate 26.
  • the inner lid 25 and the partition plate 26 may not be provided.
  • the battery 3 is inserted between the partition plates 26 of the case body 21.
  • a plurality of metal bus bars 4 are placed on the inner lid 25.
  • the inner lid 25 is arranged on the terminal surface on which the terminal 32 of the battery 3 is provided, the adjacent terminals 32 of the adjacent batteries 3 are connected by the bus bar 4, and the batteries 3 are connected in series.
  • the BMU accommodating portion 23 has a box shape, and has a protruding portion 23a protruding in a square shape on the outer side at the central portion of the long side surface.
  • a pair of external terminals 5 and 5 made of a metal such as a lead alloy and having different polarities are provided on both sides of the protruding portion 23a of the lid portion 22.
  • the BMU 6 includes an information processing unit 60, a voltage measurement unit 8, and a current measurement unit 9 mounted on a substrate.
  • the battery 3 and the BMU 6 are connected by accommodating the BMU 6 in the BMU accommodating part 23 and covering the BMU accommodating part 23 with the cover 24.
  • the information processing unit 60 includes a CPU 62 and a memory 63.
  • the memory 63 stores an SOC estimation program 63a according to the present embodiment, and a table 63b in which a full charge SOC-OCV curve and a discharge SOC-OCV curve are stored.
  • the SOC-OCV curve is not limited to being stored in the table 63b, and may be stored in the memory 63 as an intermediate expression.
  • a full charge SOC-OCV curve and a discharge SOC-OCV curve are obtained by actual measurement at predetermined time intervals. As the battery 3 deteriorates, the charge / discharge SOC-OCV curve is updated. Note that the charge / discharge SOC-OCV curve may be measured each time the battery 3 is used.
  • the SOC estimation program 63a is provided in a state stored in a computer-readable recording medium 70 such as a CD-ROM, DVD-ROM, or USB memory, and is stored in the memory 63 by being installed in the BMU 6.
  • the SOC estimation program 63a may be acquired from an external computer (not shown) connected to the communication network and stored in the memory 63.
  • the CPU 62 executes an SOC estimation process to be described later in accordance with the SOC estimation program 63a read from the memory 63.
  • the voltage measuring unit 8 is connected to both ends of the battery 3 via voltage detection lines, and measures the voltage value of each battery 3 at predetermined time intervals.
  • the current measuring unit 9 measures the current value flowing through the battery 3 via the current sensor 7 at predetermined time intervals.
  • External terminals 5 and 5 of the battery module 1 are connected to a load 11 such as an engine starter motor and electrical components.
  • the ECU (Electronic Control Unit) 10 is connected to the BMU 6 and the load 11.
  • 16 and 17 are flowcharts showing the procedure of the SOC estimation process performed by the CPU 62.
  • the CPU 62 repeats the processing from S1 at a predetermined interval.
  • CPU62 acquires the voltage value and electric current value between the terminals of the battery 3 (S1). Since the lower limit voltage value and the ultimate voltage value described later are OCV, it is necessary to correct the acquired voltage value to OCV when the current amount of the battery 3 is large.
  • the correction value to OCV is obtained by estimating the voltage value when the current value is zero using a regression line from a plurality of voltage value and current value data.
  • the acquired voltage value can be regarded as an OCV.
  • the CPU62 determines whether the absolute value of an electric current value is more than a threshold value (S2).
  • the threshold value is set in order to determine whether the state of the battery 3 is a charged state, a discharged state, or a resting state. If the CPU 62 determines that the absolute value of the current value is not equal to or greater than the threshold value (S2: NO), the process proceeds to S13.
  • the CPU 62 determines whether the current value is greater than 0 (S3). When the current value is larger than 0, it can be determined that the state of the battery 3 is the charged state. If the CPU 62 determines that the current value is not greater than 0 (S3: NO), the process proceeds to S9.
  • the CPU 62 determines whether the current value is greater than 0 (S3: YES), it determines whether the voltage value is equal to or higher than the lower limit voltage value (S4). If the CPU 62 determines that the voltage value is not greater than or equal to the lower limit voltage value (S4: NO), the process proceeds to S8.
  • the CPU 62 determines that the voltage value is greater than or equal to the lower limit voltage value (S4: YES). If the CPU 62 determines that the voltage value is greater than or equal to the lower limit voltage value (S4: YES), the CPU 62 turns on the voltage reference flag (S5). The CPU 62 determines whether or not the acquired voltage value is larger than the previous reached voltage value (S6). If the CPU 62 determines that the voltage value is not greater than the previous reached voltage value (S6: NO), the process proceeds to S8.
  • the CPU 62 determines that the voltage value is larger than the previous ultimate voltage value (S6: YES)
  • the CPU 62 updates the voltage value to the ultimate voltage value in the memory 63 (S7).
  • CPU62 estimates SOC by electric current integration (S8), and complete
  • the CPU 62 determines whether or not the voltage value is less than the lower limit voltage value in S9 (S9). If the CPU 62 determines that the voltage value is not less than the lower limit voltage value (S9: NO), the process proceeds to S12. When the CPU 62 determines that the voltage value is less than the lower limit voltage value (S9: YES), the CPU 62 turns off the voltage reference flag (S10). The CPU 62 resets the ultimate voltage value (S11). The CPU 62 estimates the SOC by current integration (S12) and ends the process.
  • the CPU 62 determines whether or not the voltage reference flag is on (S13). If the CPU 62 determines that the voltage reference flag is not on (S13: NO), the process proceeds to S16.
  • the CPU 62 determines whether or not the set time has elapsed since it was determined to be in the dormant state in the previous S2 (S14). As the set time, a sufficient time for considering the acquired voltage value as the OCV is obtained in advance by an experiment. It is determined whether or not the time has been exceeded based on the number of acquisitions and the acquisition interval of the current value after determining that it is in a resting state. Thereby, the SOC can be estimated with higher accuracy in the resting state. If the CPU 62 determines that the set time has not elapsed (S14: NO), the process proceeds to S18. In S18, the CPU 62 estimates the SOC by current integration and ends the process.
  • the acquired voltage value can be regarded as an OCV.
  • the CPU 62 reads the charge / discharge SOC-OCV curve from the table 63b (S15).
  • the CPU 62 generates a reference SOC-OCV curve (S16).
  • the CPU 62 sets the discharge SOC-OCV curve on the horizontal axis so that the first point corresponding to the ultimate voltage value on the discharge SOC-OCV curve overlaps the second point corresponding to the ultimate voltage value on the charge SOC-OCV curve. Move in parallel. That is, it is translated by ⁇ SOC. Then, a curve is cut from the lower limit voltage value to the ultimate voltage value to generate a reference SOC-OCV curve.
  • the CPU 62 reads the SOC corresponding to the voltage value acquired in S1 in the reference SOC-OCV curve, estimates the SOC (S17), and ends the process.
  • the voltage value rises and falls, that is, the high inflection point among the inflection points switched from charging to discharging is set to the ultimate voltage value.
  • the voltage value acquired by the CPU 62 from the voltage measuring unit 8 varies somewhat depending on the current value. Therefore, the voltage value can be corrected by obtaining a correction coefficient through experiments.
  • the hysteresis is small (substantially no hysteresis), and the SOC is determined based on the reference SOC-OCV curve and the current voltage value in the range from the lower limit voltage value to the reached voltage value. Therefore, the accuracy of SOC estimation is good. Therefore, the OCV reset can be performed with high accuracy.
  • the SOC can be estimated in both charging and discharging. By generating the reference SOC-OCV curve by setting the inflection point of the voltage value rise / fall to the ultimate voltage value, the SOC can be estimated based only on the voltage value history when charging / discharging is repeated in a complicated pattern. . Further, only when the acquired voltage value exceeds the previous reached voltage value, the reached voltage value is updated, so that the SOC-OCV curve is selected based on the final voltage value at the time of charging with higher accuracy. The SOC can be estimated.
  • the reference SOC-OCV curve is generated by translating the discharge SOC-OCV curve by ⁇ SOC based on the ultimate voltage value stored in the memory 63.
  • a reference SOC-OCV curve corresponding to all ultimate voltage values is generated from one discharge SOC-OCV curve. It is not necessary to store the reference SOC-OCV curve in the memory 63 by actual measurement for each ultimate voltage value. That is, a reference SOC-OCV curve corresponding to each ultimate voltage value can be easily obtained from the lower limit voltage value. Only the full charge / discharge SOC-OCV curve is actually measured, and the amount of work is significantly reduced.
  • the accuracy of SOC estimation is improved.
  • the reference SOC-OCV curve is acquired according to the deterioration of the battery 3, only the full charge / discharge SOC-OCV curve is actually measured, and the work amount during the use period of the battery 3 is remarkably reduced. Since it can be estimated from the SOC-OCV curve, the amount of electricity stored is not limited to SOC, and the amount of current energy stored in the battery 3 such as the amount of power can be estimated.
  • FIGS 18 and 19 are flowcharts showing the procedure of the SOC estimation process performed by the CPU 62.
  • the CPU 62 repeats the processing from S21 at a predetermined interval.
  • CPU62 acquires the voltage value and electric current value between the terminals of the battery 3 (S21).
  • CPU62 determines whether the absolute value of an electric current value is more than a threshold value (S22).
  • the threshold value is set in order to determine whether the state of the battery 3 is a charged state, a discharged state, or a resting state. If the CPU 62 determines that the absolute value of the current value is not equal to or greater than the threshold value (S22: NO), the process proceeds to S33.
  • the CPU 62 determines whether the current value is greater than 0 (S23). When the current value is larger than 0, the battery 3 is in a charged state. If the CPU 62 determines that the current value is not greater than 0 (S23: NO), the process proceeds to S29. When determining that the current value is larger than 0 (S23: YES), the CPU 62 determines whether or not the voltage value is larger than the previous reached voltage value (S24). The voltage value may be corrected by, for example, estimating a value when the current value is zero using a regression line from a plurality of voltage value and current value data. If the CPU 62 determines that the voltage value is not greater than the previous voltage value (S24: NO), the process proceeds to S26.
  • the CPU 62 determines that the voltage value is larger than the previous reached voltage value (S24: YES)
  • the CPU 62 updates the voltage value to the reached voltage value (S25).
  • CPU62 determines whether a voltage value is more than a lower limit voltage value (S26). If the CPU 62 determines that the voltage value is not equal to or greater than the lower limit voltage value (S26: NO), the CPU 62 estimates the SOC by current integration (S30) and ends the process.
  • the CPU 62 determines that the voltage value is equal to or higher than the lower limit voltage value (S26: YES)
  • the CPU 62 reads the charge / discharge SOC-OCV curve from the table 63b (S27).
  • the CPU 62 generates a reference SOC-OCV curve (S28).
  • the CPU 62 sets the discharge SOC-OCV curve on the horizontal axis so that the first point corresponding to the ultimate voltage value on the discharge SOC-OCV curve overlaps the second point corresponding to the ultimate voltage value on the charge SOC-OCV curve. Move in parallel. That is, it is translated by ⁇ SOC. Then, a curve is cut from the lower limit voltage value to the ultimate voltage value to generate a reference SOC-OCV curve.
  • the CPU 62 reads the SOC from the current OCV to estimate the SOC (S29), and ends the process.
  • the CPU 62 calculates the current OCV from the voltage value and current value acquired in S21.
  • the OCV can be calculated by estimating a voltage value when the current value is zero using a regression line from a plurality of voltage value and current value data. When the current value is as small as the dark current value, the acquired voltage value can be read as OCV.
  • the CPU 62 determines whether or not the voltage value is equal to or higher than the lower limit voltage value in S29 (S31).
  • the CPU 62 determines that the voltage value is greater than or equal to the lower limit voltage value (S31: YES)
  • the CPU 62 estimates the SOC by referring to the voltage in the same manner as described above (S32).
  • the CPU 62 resets the ultimate voltage value (S33).
  • the CPU 62 estimates the SOC by current integration (S34) and ends the process.
  • the CPU 62 determines whether or not the voltage value is equal to or higher than the lower limit voltage value (S35). If the CPU 62 determines that the voltage value is not greater than or equal to the lower limit voltage value (S36: NO), the process proceeds to S36. When the CPU 62 determines that the voltage value is equal to or higher than the lower limit voltage value (S36: YES), the CPU 62 determines whether or not the set time has elapsed since the last time that it was determined to be in the dormant state in S22 (S36).
  • the CPU 62 determines that the set time has not elapsed (S36: NO), the process proceeds to S38.
  • the CPU 62 estimates the SOC by current integration (S38) and ends the process.
  • the acquired voltage value can be regarded as an OCV, and the SOC is estimated by referring to the voltage in the same manner as described above (S37), and the process ends.
  • the SOC can be estimated in real time during charge / discharge.
  • the SOC is estimated based on the reference SOC-OCV curve and the current voltage value in the range from the lower limit voltage value to the ultimate voltage value substantially free of hysteresis. Therefore, the accuracy of SOC estimation is good.
  • the discharge SOC-OCV curve stored in the table 63b is translated by ⁇ SOC to generate a reference SOC-OCV curve.
  • a reference SOC-OCV curve corresponding to all ultimate voltage values is generated from one discharge SOC-OCV curve. It is not necessary to store the reference SOC-OCV curve in the memory 63 by actual measurement for each ultimate voltage value.
  • a reference SOC-OCV curve corresponding to each ultimate voltage value can be easily obtained from the lower limit voltage value. Only the full charge / discharge SOC-OCV curve is actually measured, and the amount of work is significantly reduced. Compared with a case where a curve to be positioned between adjacent measured SOC-OCV curves is obtained by interpolation calculation, the accuracy of SOC estimation is improved.
  • the reference SOC-OCV curve is acquired according to the deterioration of the battery 3, only the full charge / discharge SOC-OCV curve is actually measured, and the work amount during the use period of the battery 3 is remarkably reduced.
  • the amount of electricity stored is not limited to SOC, and the amount of current energy stored in the battery 3 such as the amount of power can be estimated.
  • the SOC can be estimated in both charging and discharging. Even when charging / discharging is repeated in a complicated pattern, the SOC can be estimated only from the history of the voltage value. Since the voltage value can be used, the amount of stored electricity is not limited to the SOC, and the amount of current energy stored in the battery 3 such as the amount of power can be estimated.
  • the power storage amount estimation device generates two or more electrochemical reactions according to the charge / discharge transition, and the power storage amount ⁇ voltage value according to the charge transition, which is shown when one electrochemical reaction occurs.
  • the charge characteristics and the storage element-voltage value discharge characteristics according to the transition of discharge are smaller than the hysteresis when other electrochemical reactions occur, and the storage element including at least one of the positive electrode and the negative electrode contains an active material.
  • An estimation unit is provided that estimates the amount of electricity stored using the voltage value characteristics.
  • the charged amount is calculated based on the voltage reference charged amount-voltage value characteristic.
  • the discharge electric quantity of one electrochemical reaction in this region can be regarded as the charge electric quantity of one electrochemical reaction. That is, the same voltage reference charged amount-voltage value characteristic can be used when the charged amount is estimated in the charged state and the discharged state.
  • a storage amount-voltage value charge characteristic and a storage amount-voltage value discharge characteristic are acquired.
  • the voltage reference storage amount-voltage value characteristic can be easily obtained.
  • the amount of electricity stored in an electricity storage element having an active material having a high capacity and having an electricity storage amount-voltage value characteristic exhibiting hysteresis can be estimated easily.
  • the amount of electricity stored is not limited to the SOC, and the amount of current energy stored in the electricity storage element such as the amount of power can be estimated. Based on the charge / discharge curve, the dischargeable energy up to SOC 0% and the charge energy required up to SOC 100% can be predicted.
  • the storage amount-voltage value discharge characteristic is expressed as the storage amount-voltage value charging characteristic at the same voltage value and The storage amount is estimated based on the difference between the storage amount and the voltage value discharge characteristic, and the voltage reference storage amount-voltage value characteristic obtained by moving toward the storage amount-voltage value charging characteristic.
  • a storage amount-voltage value charge characteristic and a storage amount-voltage value discharge characteristic are acquired.
  • the difference between the storage amounts of both characteristics at the same voltage value ( ⁇ storage amount) corresponds to another electrochemical reaction.
  • One electrochemical reaction and the other electrochemical reaction occur substantially independently.
  • the reaction amount of the other electrochemical reaction corresponds to the ⁇ storage amount, and does not affect one electrochemical reaction.
  • the difference between the storage amount-voltage value charge characteristics and the storage amount-voltage value discharge characteristics at the same voltage value, and the storage amount-voltage value discharge characteristics are directed to the storage amount-voltage value charge characteristics. To obtain a voltage reference storage amount-voltage value characteristic.
  • the voltage reference storage amount-voltage value characteristic starting from each voltage value is moved from the same storage amount-voltage value discharge characteristic toward the storage amount-voltage value charging characteristic based on the same one electrochemical reaction. And has a shape cut out with the voltage value of each starting point as the upper end. According to the above configuration, the accuracy of estimation of the charged amount is better.
  • the voltage acquisition unit that acquires the voltage value of the storage element and the voltage value acquired by the voltage acquisition unit are higher than the lower limit voltage value at which the presence or absence of hysteresis is substantially switched.
  • a setting unit that sets an ultimate voltage value based on a later voltage value, and the same voltage value is preferably the ultimate voltage value.
  • the voltage reference storage amount-voltage value characteristic is generated by setting the reached voltage value based on the rise and fall of the voltage value. Even when charging / discharging is repeated with a complicated pattern, it is possible to generate a voltage reference stored amount-voltage value characteristic based only on a history of voltage values and estimate the stored amount.
  • the estimation unit obtains the movement storage amount-voltage value characteristic when the voltage value acquired by the voltage acquisition unit is between the lower limit voltage value and the ultimate voltage value. It is preferable to estimate the power storage amount with reference to.
  • the setting unit stores the reached voltage value in a storage unit, and when the voltage value acquired by the voltage acquisition unit is greater than the reached voltage value previously stored in the storage unit, It is preferable to update the acquired voltage value to the ultimate voltage value.
  • the storage amount can be estimated with high accuracy.
  • the storage amount is preferably SOC.
  • the storage amount estimation device can accurately estimate the state of charge of a storage element using an electrode material having hysteresis, in which OCV and SOC do not correspond one to one, without requiring a special sensor or additional parts. it can.
  • the power storage module includes a plurality of power storage elements and any one of the above-described power storage amount estimation devices.
  • a vehicle power storage module and an industrial power storage module typically have a plurality of power storage elements connected in series.
  • a plurality of power storage elements may be connected in series and in parallel.
  • the power storage module is suitably used as a power source for EVs and PHEVs, which have a particularly high demand for high capacity.
  • the storage amount estimation method causes two or more electrochemical reactions according to the charge / discharge transition, and the charge amount-voltage value charge according to the charge transition, which is shown when one electrochemical reaction occurs.
  • a method for estimating an amount of electricity stored wherein a voltage reference storage amount-voltage obtained based on the amount of electricity stored-voltage value discharge characteristic when the one electrochemical reaction occurs more than the other electrochemical reaction. The value characteristic is acquired, and the charged amount is estimated based on the voltage reference charged amount-voltage value characteristic.
  • the charged amount is calculated based on the voltage reference charged amount-voltage value characteristic.
  • the discharge electric quantity of one electrochemical reaction in this region can be regarded as the charge electric quantity of one electrochemical reaction. That is, the same voltage reference charged amount-voltage value characteristic can be used when the charged amount is estimated in the charged state and the discharged state.
  • a storage amount-voltage value charge characteristic and a storage amount-voltage value discharge characteristic are acquired.
  • the voltage reference storage amount-voltage value characteristic can be easily obtained. Only the storage amount-voltage value discharge characteristics and the storage amount-voltage value charging characteristics are actually measured, and the amount of work is small. Compared to the case where the voltage reference storage amount-voltage value characteristic to be positioned between adjacent voltage reference storage amount-voltage value characteristics is obtained by interpolation and compensated, the voltage reference storage amount corresponding to each reached voltage value -Since the voltage value characteristic reference is generated, the accuracy of the charged amount estimation is improved. When acquiring the voltage reference storage amount-voltage value characteristic according to the deterioration of the storage element, only the storage amount-voltage value discharge characteristic and the storage amount-voltage value charge characteristic are actually measured. The amount of work is small. The amount of electricity stored in an electricity storage element having an active material having a high capacity and having an electricity storage amount-voltage value characteristic exhibiting hysteresis can be estimated easily.
  • the charged amount can be estimated.
  • the inflection point related to the rise and fall of the voltage value is set to the ultimate voltage value, and the charged amount-voltage value characteristic is selected. Even when charging / discharging is repeated in a complicated pattern, the amount of stored electricity can be estimated only from the history of voltage values. Since the voltage value can be used, the amount of electricity stored is not limited to the SOC, and the amount of current energy stored in the electricity storage element such as the amount of power can be estimated.
  • the storage amount estimation method described above sets the reached voltage value based on the voltage value after the acquired voltage value becomes higher than the lower limit voltage value at which the presence / absence of hysteresis is substantially switched.
  • the storage amount difference between the storage amount-voltage value discharge characteristics and the storage amount-voltage value charge characteristics, and the storage amount-voltage value discharge characteristics are moved toward the storage amount-voltage value charge characteristics side.
  • a storage amount-voltage value charge characteristic and a storage amount-voltage value discharge characteristic are acquired.
  • the difference between the storage amounts of both characteristics at the same voltage value ( ⁇ storage amount) corresponds to another electrochemical reaction.
  • the reaction amount of the other electrochemical reaction corresponds to the ⁇ storage amount, and does not affect one electrochemical reaction. Therefore, the voltage reference storage amount-voltage value characteristic can be easily obtained by correcting with the ⁇ storage amount based on the storage amount-voltage value discharge characteristic in which one electrochemical reaction occurs. That is, the voltage reference storage amount-voltage value characteristic starting from each voltage value is moved from the same storage amount-voltage value discharge characteristic toward the storage amount-voltage value charging characteristic based on the same one electrochemical reaction.
  • the voltage reference storage amount-voltage value characteristic is generated by setting the reached voltage value based on the increase / decrease of the voltage value. Even when charging / discharging is repeated with a complicated pattern, it is possible to generate a voltage reference stored amount-voltage value characteristic based only on a history of voltage values and estimate the stored amount. Then, in the range from the lower limit voltage value to the reached voltage value where one electrochemical reaction occurs and hysteresis is small, the charged amount is estimated based on the voltage reference charged amount-voltage value characteristic and the current voltage value. Therefore, the accuracy of estimating the amount of stored electricity is good.
  • the computer program generates two or more electrochemical reactions according to the transition of charge / discharge, and the amount of charge-voltage value charge characteristics according to the transition of charge and the transition of discharge shown when one electrochemical reaction occurs
  • the storage amount-voltage value discharge characteristic and the storage amount-voltage value charging characteristic are acquired, and it is determined whether or not the acquired voltage value is higher than a lower limit voltage value at which the presence or absence of hysteresis is substantially switched.
  • an ultimate voltage value is set, and the storage amount-voltage value release corresponding to the set ultimate voltage value is set.
  • the voltage reference storage amount-voltage value characteristic is acquired by moving the storage amount-voltage value discharge characteristic toward the storage amount-voltage value charging characteristic, and the acquired voltage value is from the lower limit voltage value to the ultimate voltage value.
  • a process of estimating the amount of electricity stored at the voltage value is executed.
  • the present invention is not limited to the contents of the above-described embodiments, and various modifications can be made within the scope of the claims. That is, embodiments obtained by combining technical means appropriately changed within the scope of the claims are also included in the technical scope of the present invention.
  • the power storage amount estimation device according to the present invention is not limited to the case where it is applied to a vehicle-mounted lithium ion secondary battery, and can also be applied to other power storage modules such as a railway regenerative power storage device and a solar power generation system.
  • the voltage value between the positive electrode terminal and the negative electrode terminal of the power storage element or the voltage value between the positive electrode terminal and the negative electrode terminal of the power storage module can be regarded as OCV.
  • the power storage element is not limited to a lithium ion secondary battery, and may be another secondary battery or an electrochemical cell having hysteresis characteristics.
  • a CMU Cell Monitoring Unit
  • the power storage amount estimation device may be a part of a power storage module in which the monitoring device 100 or the like is incorporated.
  • the power storage amount estimation device may be configured separately from a power storage element and a power storage module, and may be connected to a power storage module including a power storage element whose heat storage amount is to be estimated when the heat storage amount is estimated.
  • the heat storage amount estimation device may remotely monitor the power storage element and the power storage module.

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Abstract

L'objectif de la présente invention est de fournir un dispositif d'estimation de quantité d'électricité stockée, un module de stockage d'électricité pourvu dudit dispositif d'estimation de quantité d'électricité stockée, un procédé d'estimation de quantité d'électricité stockée et un programme d'ordinateur qui permettent d'estimer une quantité d'électricité stockée dans un élément de stockage d'électricité comprenant un matériau actif ayant une caractéristique de valeur de quantité d'électricité stockée - tension qui présente une hystérésis. Le dispositif d'estimation de quantité d'électricité stockée (6) estime une quantité d'électricité stockée d'un élément de stockage d'électricité (3) dont l'une électrode positive et/ou l'une électrode négative contiennent un matériau actif dans lequel au moins deux réactions électrochimiques se produisent en fonction d'une transition de charge et de décharge, l'hystérésis entre une caractéristique de charge de valeur de quantité d'électricité stockée - tension et une caractéristique de décharge de valeur de quantité d'électricité stockée - tension présentée lorsqu'une réaction électrochimique se produit étant inférieure à l'hystérésis lorsque l'autre réaction électrochimique se produit. Le dispositif d'estimation de quantité d'électricité stockée (6) est pourvu d'une unité d'estimation (62) qui estime la quantité d'électricité stockée à l'aide d'une caractéristique de valeur de quantité d'électricité stockée - tension de référence de valeur de tension obtenue sur la base de la caractéristique de décharge de valeur de quantité d'électricité stockée - tension si l'une des réactions électrochimiques se produit plus fréquemment que l'autre réaction électrochimique.
PCT/JP2018/013053 2017-03-29 2018-03-28 Dispositif d'estimation de quantité d'électricité stockée, module de stockage d'électricité, procédé d'estimation de quantité d'électricité stockée et programme d'ordinateur WO2018181620A1 (fr)

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US16/498,280 US11181584B2 (en) 2017-03-29 2018-03-28 Storage amount estimation device, energy storage module, storage amount estimation method, and computer program
EP18774740.7A EP3605122B1 (fr) 2017-03-29 2018-03-28 Dispositif d'estimation de quantité d'électricité stockée, module de stockage d'électricité, procédé d'estimation de quantité d'électricité stockée et programme d'ordinateur
CN201880022409.XA CN110462413B (zh) 2017-03-29 2018-03-28 蓄电量估计装置、蓄电模块、蓄电量估计方法、和记录介质

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JP7047131B2 (ja) 2019-06-24 2022-04-04 寧徳時代新能源科技股▲分▼有限公司 電池の荷電状態の修正方法、装置、システム及び記憶媒体
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EP4123322A4 (fr) * 2020-03-16 2023-12-13 Kabushiki Kaisha Toshiba Dispositif de traitement d'informations, procédé de traitement d'informations, programme d'ordinateur et système de traitement d'informations
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JP7666755B2 (ja) 2022-09-28 2025-04-22 株式会社村田製作所 二次電池の特性取得システム、および、二次電池の特性取得方法
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