WO2021205642A1 - Dispositif de commande de batterie secondaire, système de commande de batterie secondaire, bloc-batterie et procédé de commande de batterie secondaire - Google Patents

Dispositif de commande de batterie secondaire, système de commande de batterie secondaire, bloc-batterie et procédé de commande de batterie secondaire Download PDF

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Publication number
WO2021205642A1
WO2021205642A1 PCT/JP2020/016102 JP2020016102W WO2021205642A1 WO 2021205642 A1 WO2021205642 A1 WO 2021205642A1 JP 2020016102 W JP2020016102 W JP 2020016102W WO 2021205642 A1 WO2021205642 A1 WO 2021205642A1
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Prior art keywords
secondary battery
value
minimum value
mathematically equivalent
soh
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PCT/JP2020/016102
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English (en)
Japanese (ja)
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靖博 ▲高▼木
拳 中村
佑輔 久米
英司 遠藤
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Tdk株式会社
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Priority to PCT/JP2020/016102 priority Critical patent/WO2021205642A1/fr
Publication of WO2021205642A1 publication Critical patent/WO2021205642A1/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
    • 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 secondary battery control device, a secondary battery control system, a battery pack, and a secondary battery control method.
  • SOC State of Charge
  • SOH State of Health
  • SOC is an index indicating the state of charge (remaining capacity) of the secondary battery.
  • SOC is the ratio of the remaining capacity to the fully charged capacity.
  • SOH is an index indicating the deterioration state of the battery.
  • SOH is the ratio of the full discharge capacity at the time of deterioration to the initial full discharge capacity.
  • Patent Document 1 the aged deterioration of the battery is based on the open circuit voltage value and the integrated current value acquired when the charge rate of the battery is within the non-his region which is the charge rate range in which significant hysteresis does not occur.
  • An in-vehicle battery system for estimating is disclosed.
  • Patent Document 2 describes the change amount dV of the battery voltage V of the secondary battery with respect to the change amount dQ of the charge amount Q when the charge amount Q of the secondary battery changes during charging / discharging of the secondary battery.
  • a secondary battery system including a dV / dQ calculating means for calculating a value of dV / dQ which is a ratio is disclosed.
  • Patent Document 2 describes a feature point appearing on a Q-dV / dQ curve representing the relationship between the value of the stored amount Q and the value of the dV / dQ, or the value of the battery voltage V and the dV / dQ. It is disclosed that the state of the secondary battery system is detected by using the feature points appearing on the V-dV / dQ curve showing the relationship with the value.
  • Patent Document 3 describes a first acquisition unit for acquiring the number of integrated cycles or an integrated capacity, a second acquisition unit for acquiring a voltage increase width or a voltage increase rate, an amount of change in open circuit voltage, an amount of change in voltage increase width, or A lithium ion secondary battery life estimation device including a first calculation unit for calculating the amount of change in the voltage rise rate and a second calculation unit for calculating the remaining capacity is disclosed.
  • the present invention has been made in view of the above problems, and provides a secondary battery control device capable of estimating a deteriorated state of a secondary battery with high accuracy, a secondary battery control system including the control system, and a battery pack.
  • the purpose is.
  • Another object of the present invention is to provide a method for controlling a secondary battery, which can estimate the deteriorated state of the secondary battery with high accuracy.
  • the maximum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charging voltage of the secondary battery is within the range of 3.65 V or more and less than 3.90 V.
  • the minimum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charging voltage of the secondary battery is within the range of 3.65 V or more and less than 3.90 V.
  • (dQ / dV B2 ) be the minimum value appearing in or the dQ / dV value at a point mathematically equivalent to the minimum value.
  • the maximum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charging voltage of the secondary battery is within the range of 3.90 V or more and less than 4.10 V.
  • (dQ / dV P3 ) be the maximum value appearing in or the dQ / dV value at a point mathematically equivalent to the maximum value.
  • the minimum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charging voltage of the secondary battery is within the range of 3.90 V or more and less than 4.10 V.
  • D the difference between the peak top dQ / dV and the peak bottom dQ / dV on the V ⁇ dQ / dV curve.
  • N SOH AX + B ... (1)
  • X is dQ / dV + (0.1 * D) at the peak bottom and dQ / dV- (0.1 * D) at the peak top on the V ⁇ dQ / dV curve.
  • the peak top is (dQ / dV P2 )
  • the peak bottom is (dQ / dV B1 ) or (dQ / dV B2 )
  • the peak top is (dQ / dV B2).
  • the peak bottom is (dQ / dV B2 ) or (dQ / dV B3 ).
  • the constant of A is based on the relationship between the X in the calibration sample and the degree of deterioration of the calibration sample. It is the slope of the regression line obtained by using the minimum square method obtained in advance.
  • the constant of B is a section of the regression line. A is 5 or more and 120 or less. B is ⁇ 41 or more and 77 or less. )
  • a dQ / dV calculation means for calculating the dQ / dV and obtaining the V ⁇ dQ / dV curve, and The control device for a secondary battery according to [1], further comprising a SOH correction means for correcting the degree of deterioration SOH of the secondary battery to N SOH obtained by the above formula (1).
  • a secondary battery control system including the secondary battery control device according to [1] or [2] and the secondary battery.
  • the secondary battery has a positive electrode and a negative electrode, and has a positive electrode and a negative electrode.
  • the positive electrode contains one or more of LiMO 2 (M is a transition metal element containing one or more selected from the group consisting of Co, Ni, Al, Mn and Fe) as a positive electrode active material.
  • a secondary battery pack comprising the control system for the secondary battery according to any one of [3] to [5] and a housing for accommodating the control system.
  • the maximum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charging voltage of the secondary battery is within the range of 3.65 V or more and less than 3.90 V.
  • the minimum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charging voltage of the secondary battery is within the range of 3.65 V or more and less than 3.90 V.
  • (dQ / dV B2 ) be the minimum value appearing in or the dQ / dV value at a point mathematically equivalent to the minimum value.
  • the maximum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charging voltage of the secondary battery is within the range of 3.90 V or more and less than 4.10 V.
  • (dQ / dV P3 ) be the maximum value appearing in or the dQ / dV value at a point mathematically equivalent to the maximum value.
  • the minimum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charging voltage of the secondary battery is within the range of 3.90 V or more and less than 4.10 V.
  • D the difference between the peak top dQ / dV and the peak bottom dQ / dV on the V ⁇ dQ / dV curve.
  • N SOH AX + B ... (1)
  • X is dQ / dV + (0.1 * D) at the peak bottom and dQ / dV- (0.1 * D) at the peak top on the V ⁇ dQ / dV curve.
  • the peak top is (dQ / dV P2 )
  • the peak bottom is (dQ / dV B1 ) or (dQ / dV B2 )
  • the peak top is (dQ / dV B2).
  • the peak bottom is (dQ / dV B2 ) or (dQ / dV B3 ).
  • the constant of A is based on the relationship between the X in the calibration sample and the degree of deterioration of the calibration sample. It is the slope of the regression line obtained by using the minimum square method obtained in advance.
  • the constant of B is a section of the regression line. A is 5 or more and 120 or less. B is ⁇ 41 or more and 77 or less. )
  • the degree of deterioration SOH of the secondary battery calculated from the measured value of the charging voltage of the secondary battery is corrected to the N SOH obtained by the formula (1). Therefore, a SOH value with a small error can be obtained. Since the control system and the secondary battery pack of the present invention include the control device of the secondary battery of the present invention, the deterioration state of the secondary battery can be estimated with high accuracy. Since the reliability of the secondary battery is further improved by the present invention, the present invention contributes to the achievement of the sustainable goal of stable energy supply.
  • FIG. 1 is a block diagram showing an example of a battery pack according to an embodiment of the present invention.
  • FIG. 2 is a graph showing an example of the V ⁇ dQ / dV curve of the secondary battery 4 provided in the battery pack shown in FIG.
  • FIG. 3 is a graph showing a part of the V ⁇ dQ / dV curve of the calibration sample.
  • FIG. 4 is a schematic cross-sectional view showing an example of the secondary battery 4 provided in the battery pack shown in FIG.
  • FIG. 5 is a flowchart showing an example of a procedure for verifying the SOH corrected by the control method of the secondary battery of the present embodiment.
  • FIG. 1 is a block diagram showing an example of a battery pack according to an embodiment of the present invention.
  • the battery pack 1 includes a control system 2 and a housing 3 that houses the control system 2.
  • the control system 2 includes a secondary battery 4 and a control device 5. Signal communication is performed between the secondary battery 4 and the control device 5.
  • the signal communication may be wired or wireless.
  • the secondary battery 4 is, for example, a lithium secondary battery. The specific configuration of the secondary battery 4 will be described later.
  • the secondary battery 4 has at least one battery cell 41.
  • the secondary battery 4 provided in the battery pack 1 shown in FIG. 1 has a plurality of battery cells 41, 41, ....
  • the secondary battery 4 deteriorates with repeated charging and discharging.
  • SOH is an index indicating a deteriorated state of the secondary battery 4.
  • SOH is expressed as a ratio (%) of the full discharge capacity (Ah) at the time of deterioration to the initial full discharge capacity (Ah).
  • the control device 5 is a controller that controls the secondary battery 4, for example, a microcomputer. As shown in FIG. 1, the control device 5 includes a dQ / dV calculation means 51, a SOH correction means 52, a memory 53 (recording medium), and a CPU 54.
  • the memory 53 stores a computer-readable program for executing the control method of the secondary battery 4, which will be described later.
  • the CPU 54 executes the program stored in the memory 53.
  • the CPU 54 comprehensively controls the control device 5 and reads the program from the memory 53 to execute the control method of the secondary battery 4 and the like.
  • the control device 5 has a known SOC calculation means (not shown).
  • the control device 5 includes a known current integrating means for calculating the current integrated value (not shown), a known electric amount calculating means for calculating the amount of electricity (not shown), and a known voltage detecting means for detecting the discharge voltage (not shown). ) May have.
  • the dQ / dV calculation means 51 monitors (monitors) the charging voltage and the amount of electricity stored in the secondary battery 4 measured and input by a known measuring device. Further, the dQ / dV calculation means 51 calculates dQ / dV from the amount of change in the charging voltage and the amount of change in the amount of electricity stored in the secondary battery 4 per unit time. dQ / dV is the ratio of the amount of change in the amount of electricity stored to the amount of change in the charging voltage of the secondary battery 4. The calculation of dQ / dV may be performed at the time of charging, at the time of discharging, or at the time of charging and discharging.
  • the dQ / dV calculation means 51 uses the calculated dQ / dV to obtain a V ⁇ dQ / dV curve as constant current charging characteristic information.
  • the V ⁇ dQ / dV curve is a curve showing the relationship between the charging voltage of the secondary battery 4 and dQ / dV, which is the ratio of the amount of change in the amount of electricity stored to the amount of change in the charging voltage of the secondary battery 4.
  • FIG. 2 is a graph showing an example of the V ⁇ dQ / dV curve of the secondary battery 4 provided in the battery pack shown in FIG.
  • the horizontal axis is the charging voltage of the secondary battery
  • the vertical axis is dQ / dV.
  • the V-dQ / dV curve shown in FIG. 2 has a plurality of peaks. More specifically, the V-dQ / dV curve shown in FIG. 2 includes a peak top indicated by a maximum point P1, P2, P3, P4 and a peak bottom indicated by a minimum point B1, B2, B3, B4. ..
  • Each maximum point P1, P2, P3, P4 in the V-dQ / dV curve corresponds to a portion (voltage stable region) where the potential is flat in the charge / discharge curve.
  • each minimum point B1, B2, B3, B4 in the V-dQ / dV curve corresponds to a portion (voltage fluctuation region) in which the potential fluctuation is large in the charge / discharge curve.
  • the plurality of peaks in the V-dQ / dV curve are caused by the material of the positive electrode and / or the negative electrode forming the battery cell 41.
  • the maximum point P2 is the maximum associated with the voltage stable region that appears second when the charge curve when charging from the fully discharged state (low charge voltage side) is differentiated in the initial charge / discharge test of the secondary battery 4. It is a point.
  • the initial charge / discharge test indicates that the charge / discharge cycle is within 10 times.
  • the maximum point P2 is, for example, a peak based on the two-phase coexistence state of the stage 2L and the stage 2 in the stage structure of graphite when the negative electrode of the battery cell 41 contains graphite.
  • the minimum point B3 is the minimum associated with the voltage fluctuation region that appears third when the charge curve when charging from the fully discharged state (low charge voltage side) is differentiated in the initial charge / discharge test of the secondary battery 4.
  • the minimum point B3 is, for example, a peak associated with the completion of the single-phase reaction in the cubic crystal of lithium manganese oxide when the positive electrode of the battery cell 41 contains lithium manganese oxide (LMO).
  • the dQ / dV calculation means 51 calculates the following (A1) to (A6).
  • (A1) The minimum value that appears first from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charge voltage of the secondary battery is 3.0 V or more and less than 3.65 V.
  • A2 The maximum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charge voltage of the secondary battery is 3.65 V or more and less than 3.90 V.
  • the dQ / dV value (dQ / dV P2 ) at the maximum value appearing in the range of or at a point mathematically equivalent to the maximum value.
  • the minimum value that appears second from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charge voltage of the secondary battery is 3.65 V or more and less than 3.90 V.
  • the maximum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the maximum value, or the charge voltage of the secondary battery is 3.90 V or more and less than 4.10 V.
  • the minimum value that appears third from the low charge rate side, the dQ / dV value at a point mathematically equivalent to the minimum value, or the charge voltage of the secondary battery is 3.90 V or more and less than 4.10 V.
  • A6 Difference D between peak top dQ / dV and peak bottom dQ / dV on the V ⁇ dQ / dV curve.
  • the difference D is the difference from the peak bottom which is (dQ / dV B1 ) or (dQ / dV B2 ) when the peak top is (dQ / dV P2).
  • the difference D is the difference from the peak bottom which is (dQ / dV B2 ) or (dQ / dV B3 ) when the peak top is (dQ / dV P3).
  • the "mathematical equivalent value” means a value having an equivalent relationship by mathematical conversion.
  • the QdQ / dV curve is a QV curve differentiated by a voltage V. Therefore, each of the extremum points of dQ / dV is mathematically equivalent to the inflection point in the QV curve.
  • the V-dQ / dV curve can be rewritten into a Q-dQ / dV curve by mathematical conversion. For example, in the calculation of (A1) to (A6), the dQ / dV value at the extremum point (maximum point and minimum point) is changed to the dQ / dV value at the point mathematically equivalent to the extremum point. May be good.
  • dQ / dV B1 corresponds to dQ / dV at the minimum point B1
  • dQ / dV P2 corresponds to dQ / dV at the maximum point P2
  • dQ / dV B2 corresponds to dQ / dV at the maximum point P2
  • dQ / dV B2 corresponds to dQ / dV of the minimum point B2.
  • dQ / dV P3 corresponds to dQ / dV at the maximum point P3
  • dQ / dV B3 corresponds to dQ / dV at the minimum point B3.
  • (A1) to (A6) calculated by the dQ / dV calculation means 51 are sent to the SOH correction means 52.
  • the SOH correction means 52 estimates the SOH of the secondary battery 4 from the equation (1) based on (A1) to (A6).
  • the SOH correction means 52 corrects the SOH of the secondary battery 4 to N SOH , using the estimated SOH as the correction value N SOH.
  • N SOH AX + B ... (1)
  • X is dQ / dV + (0.1 * D) at the peak bottom and dQ / dV- (0.1 * D) at the peak top on the V ⁇ dQ / dV curve.
  • the peak top is (dQ / dV P2 )
  • the peak bottom is (dQ / dV B1 ) or (dQ / dV B2 )
  • the peak top is (dQ / dV B2).
  • the peak bottom is (dQ / dV B2 ) or (dQ / dV B3 ).
  • the constant of A is based on the relationship between the X in the calibration sample and the degree of deterioration of the calibration sample. It is the slope of the regression line obtained by using the minimum square method obtained in advance.
  • the constant of B is a section of the regression line. A is 5 or more and 120 or less. B is ⁇ 41 or more and 77 or less. )
  • the SOH correction means 52 in the present embodiment is used when the dQ / dV on the V ⁇ dQ / dV curve obtained from the measured value of the secondary battery 4 reaches a state corresponding to the range shown in (a) below. , Calculate X in equation (1).
  • the constants A and B in the formula (1) are constants obtained in advance from the relationship between X in the calibration sample and the degree of deterioration of the calibration sample, and are based on the results of the charge / discharge test of the calibration sample performed in advance. It is a calculated value.
  • the constants A and B are stored in the memory 53 in advance.
  • the constants A and B stored in the memory 53 are read from the memory 53 when the SOH correction means 52 corrects the SOH to N SOH.
  • the constant of A in the equation (1) is the slope of the regression line obtained by using the least squares method obtained in advance from the relationship between X in the calibration sample and the degree of deterioration of the calibration sample.
  • the constant of B in the equation (1) is an intercept of the regression line.
  • the constants A and B are obtained, for example, by the method shown below.
  • a calibration sample As the calibration sample, a sample having the same capacity and made of the same material as the secondary battery 4 actually used is prepared. The deterioration behavior of the calibration sample of the same material and the same capacity is similar to the deterioration behavior of the secondary battery 4 actually used.
  • FIG. 3 is a graph showing a part of the V ⁇ dQ / dV curve of the calibration sample.
  • the numerical value described as a legend of the V-dQ / dV curve shown in FIG. 3 is the degree of deterioration (SOH (%)) of the calibration sample.
  • the numerical value 100 described as a legend of the V-dQ / dV curve is the V-dQ / dV curve of the calibration sample in the initial state.
  • SOH degree of deterioration
  • the V-dQ / dV curve is used to obtain the corresponding dQ / dV value within the range of (a) above in the calibration sample.
  • the value of dQ / dV within the range of (a) is obtained every time the charge / discharge cycle is performed a predetermined number of times.
  • the degree of deterioration (SOH) of the calibration sample is obtained from the dQ / dV value obtained above.
  • the degree of deterioration (SOH) of the calibration sample is obtained by dividing the capacity (Ah) when fully charged to fully discharged in the number of cycles by the capacity (Ah) when fully discharged from the initial full charge.
  • the error of the regression line obtained by using the least squares method between the value of dQ / dV and the degree of deterioration of the calibration sample within the range of (a) is small.
  • the constant of A in the equation (1) is the slope of the regression line.
  • the constant of B in the equation (1) is an intercept of the regression line.
  • the constants A and B in the formula (1) are used when the value of dQ / dV of the secondary battery 4 corresponds to the range of (a).
  • the constants A and B in the equation (1) are determined by the regression line between the dQ / dV value of the calibration sample corresponding to the range of (a) and the degree of deterioration when the dQ / dV value is used. NS.
  • the value of dQ / dV of the secondary battery 4 corresponds to the range of the following (b1) to the following (b2), the following (b1) used for the constants A and B determined above.
  • the SOH correction means 52 sends the correction value corrected to N SOH obtained by the equation (1) to the secondary battery 4.
  • the deterioration degree SOH of the secondary battery 4 is replaced with N SOH.
  • Replacement of the SOH of the N SOH for example, can be performed when the N SOH is obtained in SOH correction means 52.
  • FIG. 4 is a schematic cross-sectional view showing an example of the secondary battery 4 provided in the battery pack shown in FIG.
  • the secondary battery 4 shown in FIG. 4 includes, for example, at least one battery cell 41, an exterior body 42, and an electrolytic solution (not shown).
  • the secondary battery 4 shown in FIG. 4 includes one battery cell 41 for convenience of explanation.
  • the secondary battery 4 included in the control system 2 is not limited to the example shown in FIG. 1, and may include a laminated body in which a plurality of battery cells are laminated.
  • the battery cell 41 is connected to the outside via a pair of terminals 43.
  • the exterior body 42 covers the periphery of the battery cell 41.
  • the exterior body 42 is, for example, a metal laminate film in which a metal foil 42A is coated with a resin layer 42B from both sides.
  • the electrolytic solution is housed in the exterior body 42 and impregnated in the battery cell 41.
  • the battery cell 41 includes a positive electrode 41A, a negative electrode 41B, and a separator 41C.
  • the separator 41C is sandwiched between the positive electrode 41A and the negative electrode 41B.
  • the separator 41C is, for example, a film having an electrically insulating porous structure. As the separator 41C, a known one can be used.
  • the positive electrode 41A has a positive electrode current collector 41AA and a positive electrode active material layer 41AB.
  • the positive electrode current collector 41AA is, for example, a conductive plate material.
  • the positive electrode active material layer 41AB is formed on at least one surface of the positive electrode current collector 41AA.
  • the positive electrode active material layer 41AB may be formed on both surfaces of the positive electrode current collector 41AA.
  • the positive electrode active material layer 41AB has, for example, a positive electrode active material, a conductive auxiliary material, and a binder.
  • the positive electrode active material reversibly proceeds with the occlusion and release of lithium ions, the desorption and insertion (intercalation) of lithium ions, or the doping and dedoping of lithium ions and counter anions.
  • the positive electrode 41A preferably contains one or more LiMO 2 (M is a transition metal element containing one or more selected from the group consisting of Co, Ni, Al, Mn and Fe) as the positive electrode active material. ..
  • Examples of the positive electrode active material include lithium cobalt oxide (LCO), lithium nickel cobalt manganese composite oxide (NCM), lithium nickel cobalt aluminum composite oxide (NCA), lithium manganese oxide (LMO), and lithium iron phosphate (LMO). LFP) and the like.
  • the positive electrode active material layer 41AB may contain a plurality of these positive electrode active materials.
  • the positive electrode active material is not limited to these, and known materials can be used. Known conductive auxiliary materials and binders can be used.
  • the negative electrode 41B has a negative electrode current collector 41BA and a negative electrode active material layer 41BB.
  • the negative electrode current collector 41BA is, for example, a conductive plate material.
  • the negative electrode active material layer 41BB is formed on at least one surface of the negative electrode current collector 41BA.
  • the negative electrode active material layer 41BB may be formed on both surfaces of the negative electrode current collector 41BA.
  • the negative electrode active material layer 41BB has, for example, a negative electrode active material, a conductive auxiliary material, and a binder.
  • the negative electrode active material may be any compound that can occlude and release ions, and a known negative electrode active material used in a lithium ion secondary battery can be used.
  • the negative electrode active material is, for example, graphite.
  • metallic lithium, a silicon compound, or the like may be used as the negative electrode active material.
  • the electrolytic solution is sealed in the exterior body 42 and impregnated in the battery cell 41.
  • As the electrolytic solution a known one can be used.
  • the battery pack 1 of the present embodiment has a control system 2 including a control device 5 of the secondary battery 4.
  • the control device 5 of the secondary battery 4 corrects the deterioration degree SOH of the secondary battery calculated from the measured value of the charging voltage of the secondary battery 4 to the N SOH obtained by the equation (1). Therefore, in the control device 5 of the secondary battery 4 of the present embodiment, and the battery pack 1 and the control system 2 including the control device 5, the deteriorated state of the secondary battery 4 can be estimated with high accuracy.
  • FIG. 5 is a flowchart showing an example of a procedure for verifying the SOH corrected by the control method of the secondary battery of the present embodiment.
  • the flowchart shown in FIG. 5 is executed by, for example, the CPU 54 included in the battery pack 1 shown in FIG.
  • the secondary battery 4 is obtained (step S11).
  • the secondary battery 4 is fully discharged at 25 ° C. with a constant current corresponding to 0.2 C (step S12).
  • 1C represents a current value for discharging the reference capacity of the battery in 1 hour
  • 0.2C represents a current value of 1/5 of that.
  • the battery is fully charged at 25 ° C. with a constant current corresponding to 0.2 C (step S13).
  • the control device 5 starts detecting the voltage and the current value of the secondary battery 4 at the same time as the start of charging, and obtains the integrated current value.
  • the dQ / dV calculating means 51 of the control device 5 obtains the electric energy Q from the obtained integrated current value, and calculates the value of dQ / dV. As a result, the control device 5 acquires the V ⁇ dQ / dV curve in the initial state (step S14) and records it in the memory 53. At the same time, the control device 5 records the initial full charge capacity and the SOH in the initial state in the memory 53 (step S15).
  • step S16 100 cycles of charge / discharge cycles shown below are performed on the secondary battery 4 in the initial state (step S16). That is, at 45 ° C., full discharge is performed with a constant current corresponding to 0.5 C. After that, it is fully charged with a constant current corresponding to 0.5C. This charge / discharge cycle is performed 100 cycles.
  • step S17 a full discharge (step S17) is performed at a constant current corresponding to 0.2 C at 25 ° C., and a full charge is performed again at a constant current corresponding to 0.2 C at 25 ° C. (step S18).
  • step S19 the value of dQ / dV is calculated and the V ⁇ dQ / dV curve is acquired (step S19).
  • the control device 5 compares the V-dQ / dV curve acquired in step S19 with the V-dQ / dV curve acquired in step S14 in the initial state (step S20). Then, when it is determined by the control device 5 that no change is observed between the V-dQ / dV curve acquired in step S19 and the V-dQ / dV curve acquired in step S14 in the initial state, step. Return to S16.
  • step S20 when it is determined by the control device 5 that a change is observed between the V-dQ / dV curve acquired in step S19 and the V-dQ / dV curve acquired in step S14 in the initial state.
  • the control device 5 determines that the secondary battery 4 has deteriorated, and records the SOH in the memory 53 (step S21).
  • N SOH is calculated from the value of dQ / dV in the range of (a) above and the constants A and B in the range defined by the equation (1) (step S22). Then, the control device 5 confirms that the calculated N SOH and the SOH corrected by the SOH correction means 52 match or substantially match (step S23). By the above verification procedure, it can be estimated whether or not the SOH is corrected by the control device 5.
  • a lithium ion secondary battery was manufactured as the secondary battery.
  • a positive electrode was prepared.
  • Lithium nickel cobalt manganese composite oxide (NCM) LiNi 0.33 Mn 0.33 Co 0.33 O 2
  • lithium manganese oxide (LMO) LiMn 2 O 4
  • carbon black as conductive material
  • PVDF Polyvinylidene fluoride
  • NCM which is the positive electrode active material, LMO, the conductive material, and the binder
  • NCM LMO: conductive material: binder
  • the negative electrode was prepared.
  • Graphite was prepared as the negative electrode active material
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • the positive electrode and the negative electrode prepared above were laminated via a separator.
  • a laminate of polyethylene and polypropylene was used as the separator.
  • the obtained laminate was impregnated with an electrolytic solution, sealed inside the exterior, and vacuum-sealed.
  • an electrolytic solution a solvent obtained by dissolving 1.5 mol / L of lithium hexafluorophosphate (LiPF 6 ) in a solvent in which equal amounts of ethylene carbonate (EC) and dimethyl carbonate (DEC) were mixed was used. Through the above steps, a lithium secondary battery for evaluation was produced.
  • the charge / discharge cycle was repeated 100 cycles for the lithium secondary battery for evaluation.
  • the condition of one charge / discharge was that at 25 ° C., the battery was charged to a final voltage of 4.4 V with a constant current corresponding to 0.1 C, and then discharged to 3.0 V with a constant current corresponding to 0.1 C.
  • 1C represents the current value for discharging the reference capacity of the battery in 1 hour
  • 0.1C represents the current value of 1/10 of the current value.
  • the measured SOH (%) which is the degree of deterioration of the lithium secondary battery for evaluation, was determined.
  • the actual measurement SOH is obtained by dividing the capacity (Ah) when the evaluation lithium secondary battery repeated 100 cycles from full charge to full discharge is divided by the capacity (Ah) when the initial full charge is fully discharged. rice field.
  • the dQ / dV when the actually measured value of the dQ / dV value of the lithium secondary battery for evaluation reached the position (b) shown below was obtained and designated as X.
  • the position of dQ / dV on the V ⁇ dQ / dV curve is the position (C is the constant C shown in Table 1) at the peak bottom dQ / dV + (C * D) shown in Table 1. Is the difference between the peak top dQ / dV shown in Table 1 and the peak bottom dQ / dV shown in Table 1 on the V ⁇ dQ / dV curve).
  • a calibration sample of the same capacity made of the same material as the lithium secondary battery for evaluation was prepared and a charge / discharge test was conducted.
  • a regression line was obtained by using the least squares method from the relationship between the X in the calibration sample corresponding to the position (b) and the degree of deterioration of the calibration sample.
  • Table 1 shows the constant A, which is the slope of the obtained regression line, and the constant B, which is the intercept of the regression line.
  • N SOH (%) calculated by the following formula (1) was obtained.
  • N SOH AX + B ... (1)
  • the correlation coefficient between the calculated N SOH (%) and the measured SOH (%) was obtained.
  • the results are shown in Tables 1 and 2.
  • Examples 1 to 16 had a correlation coefficient of 0.8 or more, and the correlation coefficient was higher than that of Comparative Examples 1 to 7. More specifically, in Examples 1 to 16, X in the formula (1) is dQ / dV + (0.1 * D) to peak top in which dQ / dV on the V ⁇ dQ / dV curve is the peak bottom. When the peak top is (dQ / dV P2 ), the peak bottom is (dQ / dV B1 ) or When (dQ / dV B2 ) and the peak top is (dQ / dV P3 ), the peak bottom is (dQ / dV B2 ) or (dQ / dV B3 ). Further, in Examples 1 to 16, A in the formula (1) is 5 or more and 120 or less, and B is ⁇ 41 or more and 77 or less.
  • Comparative Example 1 and Comparative Example 2 the peak top is (dQ / dV P1 ). Therefore, in Comparative Example 1 and Comparative Example 2, the error of the regression line obtained to determine the constants of A and B in the equation (1) is large, and the error from the measured SOH (%) is large (correlation coefficient). Is presumed to have become smaller). Further, in Comparative Example 3 and Comparative Example 4, the peak top is (dQ / dV P4 ), the peak bottom is (dQ / dV B4 ), the constant A is small, and the constant B is large. Therefore, in Comparative Example 3 and Comparative Example 4, it is estimated that the error from the measured SOH (%) is large (the correlation coefficient is small).

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Abstract

La présente invention concerne un dispositif de commande de batterie secondaire qui corrige l'état de santé (SOH) d'une batterie secondaire à NSOH calculé par la formule suivante. NSOH = AX + B (X représente dQ/dV sur une courbe V-dQ/dV dans le cas où dQ/dV se trouve dans la plage d'un fond de pic dQ/dV + (0,1*D) à un sommet de pic dQ/dV- (0,1*D), dans le cas où le sommet de pic est (dQ/dVP2), le fond de pic est ((dQ/dVB1) ou (dQ/dVB2), et dans le cas où le sommet de pic est (dQ/dVP3), le fond de pic est (dQ/dVB2) ou (dQ/dVB3). La constante A représente la pente d'une ligne de régression calculée par la méthode des moindres carrés précédemment calculée à partir d'une relation entre X dans des échantillons d'étalonnage et le degré de dégradation des échantillons d'étalonnage. La constante B représente une interception de la ligne de régression. A est compris entre 5 et 120. B est compris entre -41 et 77. Selon la présente invention, la fiabilité d'une batterie secondaire est améliorée. Par conséquent, la présente invention contribue à l'obtention d'une alimentation en énergie stable, qui fait partie des objectifs de développement durable.
PCT/JP2020/016102 2020-04-10 2020-04-10 Dispositif de commande de batterie secondaire, système de commande de batterie secondaire, bloc-batterie et procédé de commande de batterie secondaire WO2021205642A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022119282A1 (de) 2022-07-05 2024-01-11 GM Global Technology Operations LLC Funktionszustandsbasierter Betrieb für Fahrzeugstromquellen

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009252381A (ja) * 2008-04-01 2009-10-29 Toyota Motor Corp 二次電池システム
JP2014092471A (ja) * 2012-11-05 2014-05-19 Toyo System Co Ltd 二次電池評価方法および評価プログラム
JP2016014588A (ja) * 2014-07-02 2016-01-28 日産自動車株式会社 バッテリ管理装置
JP2016119249A (ja) * 2014-12-22 2016-06-30 株式会社日立製作所 リチウムイオン二次電池システム
JP2019056595A (ja) * 2017-09-20 2019-04-11 三菱自動車工業株式会社 二次電池システム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009252381A (ja) * 2008-04-01 2009-10-29 Toyota Motor Corp 二次電池システム
JP2014092471A (ja) * 2012-11-05 2014-05-19 Toyo System Co Ltd 二次電池評価方法および評価プログラム
JP2016014588A (ja) * 2014-07-02 2016-01-28 日産自動車株式会社 バッテリ管理装置
JP2016119249A (ja) * 2014-12-22 2016-06-30 株式会社日立製作所 リチウムイオン二次電池システム
JP2019056595A (ja) * 2017-09-20 2019-04-11 三菱自動車工業株式会社 二次電池システム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022119282A1 (de) 2022-07-05 2024-01-11 GM Global Technology Operations LLC Funktionszustandsbasierter Betrieb für Fahrzeugstromquellen

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