WO2017158923A1 - 密閉型二次電池の残容量予測方法、残容量予測システム、電池内部情報の取得方法及び電池制御方法 - Google Patents
密閉型二次電池の残容量予測方法、残容量予測システム、電池内部情報の取得方法及び電池制御方法 Download PDFInfo
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- WO2017158923A1 WO2017158923A1 PCT/JP2016/083789 JP2016083789W WO2017158923A1 WO 2017158923 A1 WO2017158923 A1 WO 2017158923A1 JP 2016083789 W JP2016083789 W JP 2016083789W WO 2017158923 A1 WO2017158923 A1 WO 2017158923A1
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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]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method, a system, a battery internal information acquisition method, and a battery control method for predicting the remaining capacity of a sealed secondary battery.
- secondary batteries represented by lithium ion secondary batteries (hereinafter sometimes referred to simply as “secondary batteries”) are not only mobile devices such as mobile phones and laptop computers, but also electric vehicles and hybrids. It is also used as a power source for electric vehicles such as cars.
- the secondary battery deteriorates by repeating the charge / discharge cycle, and it becomes difficult to accurately grasp the remaining capacity as the deterioration progresses.
- Patent Document 1 a change in battery voltage per predetermined time is sequentially measured while performing constant current charging or constant current discharging of a secondary battery, and based on the time when the change in the battery voltage is equal to or less than a predetermined value, A method for calculating the deterioration rate of the secondary battery is described.
- the battery voltage per predetermined time changes depending on the charge / discharge history up to the time of measurement, the battery voltage is mounted on an application that is used while repeating the charge / discharge cycle, for example, an electric vehicle that frequently repeats the charge / discharge cycle. Not suitable for use in the environment.
- Patent Document 2 describes a method for calculating a charge capacity by fully charging a battery once it is completely discharged and integrating the amount of current for charging at that time.
- the battery since it is rare that the battery is completely discharged in actual use, it is not suitable for use in an environment where it is used in an electric vehicle that repeatedly uses the charge / discharge cycle, for example, an electric vehicle that frequently repeats the charge / discharge cycle. Not suitable.
- Patent Document 3 the voltage and internal pressure of the secondary battery are detected, the relational data between the voltage and the internal pressure of the secondary battery that is not deteriorated, and the relational data between the internal pressure of the secondary battery and the battery capacity. Describes a method of calculating deterioration of a secondary battery using However, since the deterioration mechanism may differ depending on the environment and conditions in which the secondary battery is used, it is necessary to prepare various patterns of relational data and it is difficult to determine which pattern is applicable.
- the present invention has been made in view of the above circumstances, and its object is to provide a method and system capable of easily and accurately predicting the remaining capacity of a sealed secondary battery, and battery internal information of the sealed secondary battery. It is in providing the acquisition method and battery control method of this.
- the method for predicting the remaining capacity of a sealed secondary battery according to the present invention is the method for predicting the remaining capacity of a sealed secondary battery, wherein the sealed secondary battery is used during the charge / discharge cycle C1 prior to the time when the remaining capacity is predicted. And detecting a first curve representing the relationship between the charge / discharge capacity and deformation amount of the sealed secondary battery, and the charge / discharge capacity and deformation amount of the sealed secondary battery in a predetermined reference state A step of fitting a reference curve representing the relationship to the first curve to obtain a second curve, and a deformation amount Tm of the sealed secondary battery during a charge / discharge cycle C2 after the charge / discharge cycle C1.
- the deformation amount Tm of the secondary battery is detected during the charge / discharge cycle C2 at that time. Then, the charge / discharge capacity Qm corresponding to the deformation amount Tm is acquired based on the second curve, and the remaining capacity is predicted by the difference between the charge / discharge capacity Qd in the fully discharged state and the charge / discharge capacity Qm in the second curve.
- the second curve is obtained by fitting the reference curve to the first curve obtained in the charge / discharge cycle C1 prior to the charge / discharge cycle C2.
- the effects of deterioration due to repeated charge / discharge cycles specifically the effects of the decrease in the amount of active material contributing to charge / discharge, the capacity balance between the positive and negative electrodes due to side reactions, and gas expansion of the secondary battery are considered.
- the remaining capacity of the secondary battery can be predicted easily and with high accuracy.
- the charge / discharge cycle C1 is within the last 100 cycles of the charge / discharge cycle C2. In order to improve the prediction accuracy of the remaining capacity, it is convenient that the charge / discharge cycle C1 is as close as possible to the charge / discharge cycle C2. Therefore, the charge / discharge cycle C1 is more preferably within the last 50 cycles of the charge / discharge cycle C2, and the latest 10 cycles. Within is more preferable. The charge / discharge cycle C1 is particularly preferably immediately before the charge / discharge cycle C2.
- the expansion rate of the charge / discharge capacity corresponds to the ratio of the amount of active material used for charge / discharge in the charge / discharge cycle C1 to the amount of active material used for charge / discharge in the reference state. Therefore, using this as an index, it is possible to grasp the maintenance rate of the active material, that is, how much of the active material that contributes to charge / discharge is maintained (in other words, how much active material is deactivated) As a result, the state of the secondary battery can be obtained with higher accuracy.
- This shift amount of charge / discharge capacity corresponds to the difference between the amount of side reaction at the positive electrode (the amount of current used other than ion insertion or desorption) and the amount of side reaction at the negative electrode. Therefore, by using this as an index, it is possible to grasp the capacity balance deviation amount of the positive and negative electrodes due to the side reaction, and as a result, the state of the secondary battery can be obtained with higher accuracy.
- a polymer matrix layer is attached to the sealed secondary battery, and the polymer matrix layer contains dispersed fillers that change the external field according to deformation of the polymer matrix layer.
- the deformation of the sealed secondary battery is detected by detecting a change in the external field according to the deformation of the polymer matrix layer.
- the polymer matrix layer contains a magnetic filler as the filler, and the deformation of the sealed secondary battery is detected by detecting a change in the magnetic field as the external field.
- the change of the magnetic field accompanying the deformation of the polymer matrix layer can be detected without wiring.
- a Hall element having a wide sensitivity region can be used, highly sensitive detection can be performed over a wider range.
- the sealed secondary battery remaining capacity prediction system includes a detection sensor that detects deformation of the sealed secondary battery in the sealed secondary battery remaining capacity prediction system, and the sealed secondary battery.
- a control device for calculating a predicted value of the remaining capacity of the battery wherein the control device detects deformation of the sealed secondary battery during a charge / discharge cycle C1 prior to the time of predicting the remaining capacity, A first curve representing the relationship between the charge / discharge capacity of the sealed secondary battery and the deformation amount is obtained, and a reference curve representing the relationship between the charge / discharge capacity of the sealed secondary battery and the deformation amount in a predetermined reference state, A fitting process is performed on the first curve to obtain a second curve, a deformation amount Tm of the sealed secondary battery is detected during a charge / discharge cycle C2 after the charge / discharge cycle C1, and the sealed secondary battery Charge / discharge capacity Qm corresponding to deformation amount Tm
- the second curve obtained based on, but that is configured to determine a residual capacity difference between the charge and discharge capacity Qd
- the deformation amount Tm of the secondary battery is detected during the charge / discharge cycle C2. Then, the charge / discharge capacity Qm corresponding to the deformation amount Tm is acquired based on the second curve, and the remaining capacity is predicted by the difference between the charge / discharge capacity Qd in the fully discharged state and the charge / discharge capacity Qm in the second curve.
- the second curve is obtained by fitting the reference curve to the first curve obtained in the charge / discharge cycle C1 prior to the charge / discharge cycle C2.
- the effects of deterioration due to repeated charge / discharge cycles specifically, the decrease in the amount of active material that contributes to charge / discharge, the capacity balance between the positive and negative electrodes due to side reactions, and the effects of gas expansion of the secondary battery. Based on this, the remaining capacity of the secondary battery can be predicted easily and with high accuracy.
- the charge / discharge cycle C1 is within the last 100 cycles of the charge / discharge cycle C2. In order to improve the prediction accuracy of the remaining capacity, it is convenient that the charge / discharge cycle C1 is as close as possible to the charge / discharge cycle C2. Therefore, the charge / discharge cycle C1 is more preferably within the last 50 cycles of the charge / discharge cycle C2, and the latest 10 cycles. Within is more preferable. The charge / discharge cycle C1 is particularly preferably immediately before the charge / discharge cycle C2.
- control device is configured to be able to acquire the expansion rate of the charge / discharge capacity used when fitting the reference curve to the first curve as the maintenance rate of the active material.
- the expansion rate of the charge / discharge capacity corresponds to the ratio of the amount of active material used for charge / discharge in the charge / discharge cycle C1 to the amount of active material used for charge / discharge in the reference state. Therefore, using this as an index, it is possible to grasp the maintenance rate of the active material, that is, how much of the active material that contributes to charge / discharge is maintained (in other words, how much active material is deactivated) As a result, the state of the secondary battery can be obtained with higher accuracy.
- control device is configured to be able to acquire a charge / discharge capacity shift amount used when fitting the reference curve to the first curve as a capacity balance deviation amount of the positive and negative electrodes due to a side reaction.
- the shift amount of the charge / discharge capacity corresponds to the difference between the side reaction amount at the positive electrode and the side reaction amount at the negative electrode. Therefore, by using this as an index, it is possible to grasp the capacity balance deviation amount of the positive and negative electrodes due to the side reaction, and as a result, the state of the secondary battery can be obtained with higher accuracy.
- the detection sensor includes a polymer matrix layer attached to the sealed secondary battery and a detection unit, and the polymer matrix layer changes an external field according to deformation of the polymer matrix layer. It is preferable that the filler is dispersed and contained so that the detection unit can detect the change in the external field. Thereby, deformation of the sealed secondary battery can be detected with high sensitivity, and deterioration of the sealed secondary battery can be diagnosed with high accuracy.
- the polymer matrix layer contains a magnetic filler as the filler, and the detection unit is configured to detect a change in a magnetic field as the external field. Thereby, the change of the magnetic field accompanying the deformation of the polymer matrix layer can be detected without wiring.
- the detection unit since a Hall element having a wide sensitivity region can be used as the detection unit, highly sensitive detection can be performed over a wider range.
- the block diagram which shows an example of the system for performing the remaining capacity prediction method which concerns on this invention
- a graph showing the second curve obtained by the fitting process Graph showing the relationship between discharge time and discharge capacity Graph showing the relationship between discharge time and remaining capacity Graph showing the relationship between the discharge capacity and potential of the negative electrode half-cell and the relationship between the discharge capacity and deformation Graph showing the relationship between the discharge capacity and potential of the negative electrode half-cell after fitting
- FIG. 1 shows a system mounted on an electric vehicle such as an electric vehicle or a hybrid vehicle.
- This system includes a battery module 1 in which an assembled battery composed of a plurality of sealed secondary batteries 2 is housed in a casing.
- four secondary batteries 2 are connected in two parallel two series, but the number of batteries and the connection form are not limited to this.
- the battery pack 1 actually includes a plurality of battery modules 1.
- a plurality of battery modules 1 are connected in series, and they are housed in a casing together with various devices such as a controller.
- the casing of the battery pack is formed in a shape suitable for in-vehicle use, for example, a shape that matches the underfloor shape of the vehicle.
- the secondary battery 2 shown in FIG. 2 is configured as a cell (single cell) in which an electrode group 22 is accommodated in a sealed outer casing 21.
- the electrode group 22 has a structure in which a positive electrode 23 and a negative electrode 24 are laminated or wound through a separator 25 therebetween, and the separator 25 holds an electrolytic solution.
- the secondary battery 2 of the present embodiment is a laminated battery using a laminated film such as an aluminum laminated foil as the outer package 21, and is specifically a laminated lithium ion secondary battery having a capacity of 1.44 Ah.
- the secondary battery 2 is formed in a thin rectangular parallelepiped shape as a whole, and the X, Y, and Z directions correspond to the length direction, the width direction, and the thickness direction of the secondary battery 2, respectively.
- the Z direction is also the thickness direction of the positive electrode 23 and the negative electrode 24.
- the secondary battery 2 is provided with a detection sensor 5 that detects deformation of the secondary battery 2.
- the detection sensor 5 includes a polymer matrix layer 3 attached to the secondary battery 2 and a detection unit 4.
- the polymer matrix layer 3 contains a filler that disperses the external field according to deformation of the polymer matrix layer 3 in a dispersed manner.
- the polymer matrix layer 3 of the present embodiment is formed in a sheet shape from an elastomer material that can be flexibly deformed.
- the detector 4 detects a change in the external field. When the secondary battery 2 swells and deforms, the polymer matrix layer 3 is deformed accordingly, and a change in the external field accompanying the deformation of the polymer matrix layer 3 is detected by the detection unit 4. In this way, deformation of the secondary battery 2 can be detected with high sensitivity.
- the polymer matrix layer 3 since the polymer matrix layer 3 is attached to the outer package 21 of the secondary battery 2, the polymer matrix layer 3 can be deformed according to deformation (mainly swelling) of the outer package 21. it can.
- the polymer matrix layer 3 may be attached to the electrode group 22 of the secondary battery 2, and according to such a configuration, the polymer is changed according to deformation (mainly swelling) of the electrode group 22.
- the matrix layer 3 can be deformed.
- the deformation of the secondary battery 2 to be detected may be any deformation of the outer package 21 and the electrode group 22.
- the signal detected by the detection sensor 5 is transmitted to the control device 6, whereby information relating to the deformation of the secondary battery 2 is supplied to the control device 6.
- the control device 6 predicts the remaining capacity of the secondary battery 2 using the information, specifically based on the following steps 1 to 4 and preferably also through steps 5 and 6.
- the secondary battery 2 deteriorates by repeating the charge / discharge cycle, and it becomes difficult to accurately grasp the remaining capacity as the deterioration proceeds.
- one cycle of charging / discharging refers to, for example, from the time when the battery is started to the time when charging is completed by connecting to the charger, and does not include regenerative charging by the brake of the electric vehicle.
- an example in which the remaining capacity is predicted in the 502th charge / discharge cycle (hereinafter simply referred to as “502nd cycle”) for the secondary battery 2 that has deteriorated after 500 charge / discharge cycles. Show.
- Step 1 deformation of the secondary battery 2 is detected during the charge / discharge cycle C1 prior to the time when the remaining capacity is predicted, and a first curve representing the relationship between the charge / discharge capacity of the secondary battery 2 and the deformation amount is obtained ( Step 1).
- the charge / discharge cycle C1 is adopted from the charge / discharge cycle before the time point at which the remaining capacity is predicted, and in this embodiment, is the 501st cycle immediately before the 502nd cycle in which the remaining capacity is predicted.
- the charge / discharge capacity is a general term for a discharge capacity and a charge capacity, and in the present embodiment, an example of a discharge capacity, specifically, a discharge capacity from a fully charged state is shown.
- the graph of FIG. 4 shows the 1st curve L1 showing the relationship between the discharge capacity and deformation amount from the full charge state of the secondary battery 2 calculated
- the secondary battery 2 is placed in a thermostatic bath at 25 ° C., left still for 120 minutes, and then charged at a constant current of 4.3 V with a charging current of 1.44 A to reach 4.3 V. Thereafter, constant voltage charging was performed until the current value attenuated to 0.07 A, and then the operation of holding the open circuit state for 10 minutes and performing constant current discharging to 3.0 V with a current of 1.44 A was repeated 500 times. .
- the secondary battery 2 In the charge / discharge process at the 501st cycle, the secondary battery 2 is placed in a constant temperature bath at 25 ° C., left still for 120 minutes, and then charged at a constant current of 4.3 V with a charging current of 0.144 A to 4.3 V. After reaching, constant voltage charging was performed until the current value was attenuated to 0.07 A, and then the open circuit state was maintained for 10 minutes, and constant current discharging was performed up to 3.0 V with a current of 0.144 A. At this time, the discharge capacity from the fully charged state to the fully discharged state was 1.27 Ah.
- the horizontal axis is the discharge capacity Q with the origin at the fully charged state
- the vertical axis is the detected deformation amount T of the secondary battery 2.
- the deformation amount T of the secondary battery 2 decreases. This is because, in the charged secondary battery 2, the electrode group 22 swells (hereinafter sometimes referred to as “electrode swell”) due to the volume change of the negative electrode active material, and the electrode swell is accompanied by discharge. This is because it becomes smaller.
- the reference curve LS represents the relationship between the charge / discharge capacity of the secondary battery 2 in the predetermined reference state (in this embodiment, the discharge capacity from the fully charged state) and the deformation amount.
- the reference curve LS is obtained using, for example, the secondary battery 2 at the time of manufacture or before shipment, with the secondary battery 2 in an initial stage that has not deteriorated as a reference state. Information on the reference curve LS is obtained by the control device 6. It is stored in advance in a storage unit (not shown). In the charging / discharging process for obtaining the reference curve LS, the secondary battery 2 before shipment is placed in a constant temperature bath at 25 ° C., left for 120 minutes, and then charged at a constant current of 4.34 V with a charging current of 0.144 A.
- the electrolyte may swell as the internal pressure increases due to the decomposed gas (hereinafter sometimes referred to as “gas swell”).
- the detection sensor 5 also detects the deformation of the secondary battery 2 due to this gas expansion, but this is only reflected as the overall size of the deformation amount T and does not appear as a change accompanying an increase in the discharge capacity Q. . Therefore, in FIG. 4, the deformation amount T decreases as the discharge capacity Q increases due to the effect of electrode swelling, and even with the same discharge capacity Q, the first curve L1 is larger than the reference curve LS.
- the amount T is shown by the influence of gas swell.
- the first curve L1 and the reference curve LS have a shape including some unevenness (gradient change) as shown in FIG. 4 due to the stage change of the electrode.
- gradient change a phenomenon including some unevenness (gradient change) as shown in FIG. 4 due to the stage change of the electrode.
- graphite graphite
- the crystalline state of the graphite sequentially changes in stages as it is discharged from the fully charged state. This is because the negative electrode active material expands as the distance between the graphene layers increases stepwise with the insertion amount of lithium ions.
- the volume of the active material changes stepwise due to the stage change, which is reflected in the first curve L1 and the reference curve LS.
- the detection sensor 5 that detects the deformation of the secondary battery 2 with high sensitivity is preferable.
- the active material used for the negative electrode of the lithium ion secondary battery a material capable of electrochemically inserting and extracting lithium ions is used.
- a negative electrode containing graphite, hard carbon, soft carbon, silicon, sulfur or the like is preferably used, and among these, a negative electrode containing graphite Is more preferably used.
- the active material used for the positive electrode include LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , Li (MnAl) 2 O 4 , Li (NiCoAl) O 2 , LiFePO 4 , and Li (NiMnCo) O 2.
- the reference curve LS is fitted to the first curve L1 to obtain the second curve L2 (step 2).
- the first curve L1 is obtained in step 1
- the reference curve LS is obtained in advance in the reference state before deterioration.
- the fitting process can be performed by a general-purpose technique such as a least square method, and is incorporated in many commercially available software packages such as Solver (registered trademark) in Microsoft Excel (registered trademark). Can be implemented using existing software.
- the graph of FIG. 5 shows the second curve L2 obtained by the fitting process.
- “charge / discharge capacity enlargement ratio Xr” corresponding to the length enlargement ratio of the reference curve LS in the X-axis direction
- “ deformation amount shift amount Ys ” correspond to the shift amount of the reference curve LS in the Y-axis direction. ”Was changed.
- Xr 0.92
- Xs -0.055 Ah
- Yr 0.8
- Ys +0.01 mm.
- the length of the reference curve LS in the X-axis direction is 0.92 times
- the length in the Y-axis direction is also multiplied by 0.8
- the reference curve LS is shifted by -0.055 Ah along the X-axis direction.
- It means a shift of +0.01 mm along the Y-axis direction.
- the reference curve LS is shifted to the charge side of the charge / discharge capacity (the negative direction of the X axis in the graph of FIG. 4), but on the contrary, the discharge side of the charge / discharge capacity (of FIG. 4).
- the reference curve may be shifted in the positive direction of the X axis).
- the reference curve LS indicates the discharge capacity from the fully charged state exceeding the charging depth 100 (%) (or the charging capacity until the fully charged state exceeding the charging depth 100 (%)) and the deformation amount of the secondary battery 2. It is preferable that the remaining capacity is predicted in the vicinity of the fully charged state.
- the charging depth exceeding 100 (%) as described above is larger than the range of the charging / discharging depth assumed in actual use.
- the deformation amount Tm of the secondary battery 2 is detected during the charge / discharge cycle C2 after the charge / discharge cycle C1 (step 3).
- the charge / discharge cycle C2 in the present embodiment is the 502nd cycle, and it is desired to predict the remaining capacity during the discharge after the 501st cycle is finished and the battery is charged once (not necessarily fully charged).
- the deformation amount Tm is detected at an arbitrary timing.
- the step 3 does not need to be performed after the steps 1 and 2, and the context is not particularly limited. That is, after detecting the deformation amount Tm in the above step 3, the above steps 1 and 2 may be executed based on the data of the charge / discharge cycle C1 before the charge / discharge cycle C2.
- the charge / discharge capacity Qm corresponding to the deformation amount Tm of the secondary battery 2 is acquired based on the second curve L2, and the complete discharge state in the second curve L2 is obtained.
- the difference between the charge / discharge capacity Qd and the charge / discharge capacity Qm is obtained as the remaining capacity Qr (step 4).
- the charge / discharge capacity Qm is a predicted value of the discharge capacity when the deformation amount Tm is detected in the 502nd cycle, and the remaining capacity Qr obtained by subtracting the charge / discharge capacity Qm from the charge / discharge capacity Qd in the fully discharged state. Is a predicted value of the remaining capacity at that time.
- the charge / discharge capacity Qm is acquired based on the detected deformation amount Tm of the secondary battery 2 and the second curve L2 obtained by the fitting process, and the charge / discharge capacity Qm and the charge / discharge capacity Qd are obtained. Since the remaining capacity Qr is obtained, the influence of deterioration due to repeated charge / discharge cycles, specifically, the decrease in the amount of active material contributing to charge / discharge, the capacity balance deviation between positive and negative electrodes due to side reactions, and the secondary The remaining capacity of the secondary battery 2 can be predicted easily and with high accuracy based on the influence of gas expansion of the battery 2. By using this, for example, it is possible to predict how many km the electric vehicle can travel while the electric vehicle is traveling.
- the secondary battery 2 In the charging / discharging process when the deformation amount Tm is obtained in FIG. 5, the secondary battery 2 is placed in a constant temperature bath at 25 ° C., left for 120 minutes, and then charged at a constant current to 4.3 V with a charging current of 1.44 A. After reaching 4.3 V, constant voltage charging is performed until the current value decays to 0.07 A, and then the open circuit state is maintained for 10 minutes, and the deformation amount Tm every time 10 seconds is discharged with a current of 0.144 A. Acquired.
- FIG. 6 is a graph showing the relationship between the discharge time and discharge capacity of the secondary battery 2.
- the transition of the predicted value (discharge capacity Qm) of the discharge capacity obtained by the above method is indicated by a broken line L3, and the transition of the actually discharged capacity is indicated by a solid line L4.
- the broken line L3 changes along the solid line L4, and it can be seen that the discharge capacity Q at the time when the deformation amount Tm is detected in the 502nd cycle can be predicted with high accuracy.
- FIG. 7 is a graph showing the relationship between the discharge time of the secondary battery 2 and the remaining capacity.
- a predicted value (remaining capacity Qr) of the remaining capacity obtained by the above method is indicated by a broken line L5, and an actual remaining capacity obtained after the end of the 502nd cycle is indicated by a solid line L6.
- the broken line L5 changes along the solid line L6, and it can be seen that the remaining capacity of the secondary battery 2 can be predicted with high accuracy.
- the charge / discharge cycle C1 is a charge / discharge cycle immediately before the charge / discharge cycle C2
- the present invention is not limited to this.
- the charge / discharge cycle C1 is as close as possible to the charge / discharge cycle C2, and the charge / discharge cycle C1 is preferably within the last 100 cycles of the charge / discharge cycle C2, More preferably within the last 50 cycles, and even more preferably within the last 10 cycles.
- the first curve includes unevenness (change in gradient) due to the stage change of the electrode as in the above-described embodiment. It is desirable to employ the charge / discharge cycle that provides the first curve as the charge / discharge cycle C1. From the same point of view, when the first curve represents the relationship between the discharge capacity and the deformation amount, the charge / discharge cycle discharged to or near the fully discharged state is adopted as the charge / discharge cycle C1, and the first curve is the charge capacity. When the relationship between the amount of deformation and the amount of deformation is expressed, it is preferable to adopt, as the charge / discharge cycle C1, a charge / discharge cycle charged from the fully discharged state or from the vicinity thereof.
- step 5 described later by further executing step 5 described later, the active material maintenance rate (and deactivation rate) can be acquired, and the deterioration state of the secondary battery 2 can be known with higher accuracy. Also, instead of or in addition, by executing step 6 described later, the amount of positive / negative capacity balance deviation due to the side reaction can be acquired, and the deterioration state of the secondary battery 2 can be known with higher accuracy. Steps 1 to 4 and steps 5 and 6 for predicting the remaining capacity are executed by the control device 6.
- the charge / discharge capacity expansion rate Xr used when fitting the reference curve LS to the first curve L1 is acquired as the active material maintenance rate (step 5).
- the stage changes when one or more lithium ions are inserted for 24 carbons and when one or more lithium ions are inserted for 12 carbons. When it is done.
- the decrease in charge / discharge capacity suggests a decrease in the amount of carbon capable of inserting and desorbing lithium ions, and the deactivation of the active material can be inferred from the expansion ratio Xr of the charge / discharge capacity.
- the active material maintenance rate is 92%, that is, the negative electrode active material contributing to charge / discharge is maintained at 92%.
- the deactivation rate of the active material determined by 1-Xr is 8%, that is, it can be diagnosed that 8% of the negative electrode active material has been deactivated and cannot be used for charge / discharge.
- the charge / discharge capacity shift amount Xs used when fitting the reference curve LS to the first curve L1 is acquired as the capacity balance deviation amount of the positive and negative electrodes due to the side reaction (step 6).
- the charge / discharge capacity shift amount Xs is a result of a shift in the capacity balance between the positive electrode 23 and the negative electrode 24, and accordingly, the difference between the side reaction amount at the positive electrode 23 and the side reaction amount at the negative electrode 24. Caused by. Therefore, it can be inferred from the shift amount Xs which side reaction amount is increased at which electrode.
- the shift amount Xs is a positive value
- the side reaction amount at the positive electrode 23 is larger than the side reaction amount at the negative electrode 24, and if the shift amount Xs is a negative value, the side reaction amount at the negative electrode 24 is positive. This is considered to be more than the side reaction amount at 23.
- the shift amount Xs was ⁇ 0.055 Ah, it can be diagnosed that the amount of side reaction at the negative electrode 24 is 0.055 Ah greater than the amount of side reaction at the positive electrode 23.
- the graph of FIG. 8 shows a curve L7 (corresponding to the fourth curve) indicating the relationship between the discharge capacity and potential of the negative electrode half-cell, and a curve L8 (corresponding to the third curve) indicating the relationship between the discharge capacity and the deformation amount. )including.
- the negative electrode half-cell refers to a battery that is combined with a negative electrode and an electrode exhibiting a constant potential such as lithium metal.
- the curve L8 is fitted to the curve L1 by the same method as that described above (step 7). Illustration of the curve (corresponding to the fifth curve) obtained by this fitting process is omitted. Applying the expansion rate Xr of charge / discharge capacity Xr and the shift amount Xs in the X-axis direction used when fitting the curve L8 to the curve L1 to the curve L7, the relationship between the discharge capacity and potential of the negative electrode half-cell after fitting is shown. A curve L9 shown (see FIG. 9, corresponding to the sixth curve) is acquired (step 8). The negative electrode potential E A m corresponding to the charge / discharge capacity Qm acquired in Step 4 is acquired based on the curve L9 (Step 9).
- the positive electrode potential E C m is acquired by subtracting the negative electrode potential E A m from the battery voltage V acquired at the deformation amount Tm (step 10). According to the above method, only the battery voltage can be acquired by the normal control method, but the potentials of the positive electrode and the negative electrode can be acquired. By using the battery so that the negative electrode potential E A m or the positive electrode potential E C m falls within a preset value (positive electrode potential value), side reactions at the positive electrode or the negative electrode can be suppressed. Thus, the battery life can be improved.
- the first curve L1 and the reference curve LS represent the relationship between the discharge capacity of the secondary battery 2 (specifically, the discharge capacity from the fully charged state) and the deformation amount.
- the present invention is not limited to this, and may represent the relationship between the charge capacity of the secondary battery (for example, the charge capacity up to a fully charged state) and the deformation amount. Even in that case, the remaining capacity of the secondary battery can be predicted by the same procedure as described above.
- the polymer matrix layer is formed on the wall portion 28 a of the exterior body 21 that faces the electrode group 22 in the thickness direction of the positive electrode 23 and the negative electrode 24, that is, the Z direction (vertical direction in FIG. 2B). 3 is pasted.
- the outer surface of the wall portion 28 a corresponds to the upper surface of the exterior body 21.
- the polymer matrix layer 3 is opposed to the electrode group 22 with the wall portion 28 a interposed therebetween, and is disposed in parallel with the upper surface of the electrode group 22. Since the electrode swelling is caused by the change in the thickness of the electrode group 22 accompanying the change in the volume of the active material, the action in the Z direction is large. Therefore, in the present embodiment in which the polymer matrix layer 3 is attached to the wall portion 28a, the electrode swelling can be detected with high sensitivity, and the remaining capacity of the secondary battery 2 can be accurately predicted.
- the polymer matrix layer 3 is attached to the electrode group 22 from the thickness direction of the positive electrode 23 and the negative electrode 24, that is, the Z direction (vertical direction in FIG. 3B).
- the Z direction vertical direction in FIG. 3B.
- the detection unit 4 is disposed at a location where a change in the external field can be detected, and is preferably affixed to a relatively rigid location that is not easily affected by the swelling of the secondary battery 2.
- the detection unit 4 is attached to the inner surface of the casing 11 of the battery module facing the wall 28a.
- the casing 11 of the battery module is formed of, for example, metal or plastic, and a laminate film may be used.
- the detection unit 4 is disposed close to the polymer matrix layer 3, but may be disposed away from the polymer matrix layer 3.
- the polymer matrix layer 3 contains a magnetic filler as the filler, and the detection unit 4 detects a change in the magnetic field as the external field.
- the polymer matrix layer 3 is preferably a magnetic elastomer layer in which a magnetic filler is dispersed in a matrix made of an elastomer component.
- the magnetic filler examples include rare earths, irons, cobalts, nickels, oxides, etc., but rare earths capable of obtaining higher magnetic force are preferable.
- the shape of the magnetic filler is not particularly limited, and may be spherical, flat, needle-like, columnar, or indefinite.
- the average particle size of the magnetic filler is preferably 0.02 to 500 ⁇ m, more preferably 0.1 to 400 ⁇ m, and still more preferably 0.5 to 300 ⁇ m. When the average particle size is smaller than 0.02 ⁇ m, the magnetic properties of the magnetic filler tend to be lowered, and when the average particle size exceeds 500 ⁇ m, the mechanical properties of the magnetic elastomer layer tend to be lowered and become brittle.
- the magnetic filler may be introduced into the elastomer after magnetization, but is preferably magnetized after being introduced into the elastomer. Magnetization after introduction into the elastomer facilitates control of the polarity of the magnet and facilitates detection of the magnetic field.
- thermoplastic elastomer a thermoplastic elastomer, a thermosetting elastomer, or a mixture thereof can be used.
- thermoplastic elastomer examples include styrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polybutadiene-based thermoplastic elastomer, polyisoprene-based thermoplastic elastomer, A fluororubber-based thermoplastic elastomer can be used.
- thermosetting elastomer examples include polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, polychloroprene rubber, nitrile rubber, diene synthetic rubber such as ethylene-propylene rubber, ethylene-propylene rubber, butyl rubber, acrylic rubber, Non-diene synthetic rubbers such as polyurethane rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, and natural rubber can be mentioned.
- a thermosetting elastomer is preferable because it can suppress the sag of the magnetic elastomer accompanying heat generation and overload of the battery. More preferred is polyurethane rubber (also referred to as polyurethane elastomer) or silicone rubber (also referred to as silicone elastomer).
- Polyurethane elastomer is obtained by reacting polyol and polyisocyanate.
- an active hydrogen-containing compound and a magnetic filler are mixed, and an isocyanate component is mixed here to obtain a mixed solution.
- a liquid mixture can also be obtained by mixing a magnetic filler with an isocyanate component and mixing an active hydrogen-containing compound. The mixed liquid is poured into a mold subjected to a release treatment, and then heated to a curing temperature and cured to produce a magnetic elastomer.
- a magnetic elastomer can be produced by adding a magnetic filler to a silicone elastomer precursor, mixing it, putting it in a mold, and then heating and curing it. In addition, you may add a solvent as needed.
- isocyanate component that can be used in the polyurethane elastomer
- compounds known in the field of polyurethane can be used.
- the isocyanate component may be modified such as urethane modification, allophanate modification, biuret modification, and isocyanurate modification.
- Preferred isocyanate components are 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, more preferably 2,4-toluene diisocyanate, 2,6-toluene diisocyanate.
- polyurethane those usually used in the technical field of polyurethane can be used.
- Polyester polyol such as polyester polyol, polycaprolactone polyol, reaction product of polyester glycol and alkylene carbonate such as polycaprolactone, and the like, and the reaction of the resulting reaction mixture with organic polyol.
- Polyester polycarbonate polyol reacted with dicarboxylic acid, esterification of polyhydroxyl compound and aryl carbonate High molecular weight polyol polycarbonate polyols obtained by the reaction can be mentioned. These may be used alone or in combination of two or more.
- Preferred active hydrogen-containing compounds are polytetramethylene glycol, polypropylene glycol, a copolymer of propylene oxide and ethylene oxide, 3-methyl-1,5-pentane adipate, more preferably a copolymer of polypropylene glycol, propylene oxide and ethylene oxide. It is a coalescence.
- the isocyanate component As a preferred combination of the isocyanate component and the active hydrogen-containing compound, as the isocyanate component, one or more of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4′-diphenylmethane diisocyanate, active hydrogen
- the contained compound include polytetramethylene glycol, polypropylene glycol, a copolymer of propylene oxide and ethylene oxide, and one or more of 3-methyl-1,5-pentaneadipate.
- a combination of 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate as the isocyanate component and polypropylene glycol and / or a copolymer of propylene oxide and ethylene oxide as the active hydrogen-containing compound. is there.
- the polymer matrix layer 3 may be a foam containing dispersed filler and bubbles.
- a general resin foam can be used as the foam, but it is preferable to use a thermosetting resin foam in consideration of characteristics such as compression set.
- the thermosetting resin foam include a polyurethane resin foam and a silicone resin foam. Among these, a polyurethane resin foam is preferable.
- the above-mentioned isocyanate component and active hydrogen-containing compound can be used for the polyurethane resin foam.
- the amount of the magnetic filler in the magnetic elastomer is preferably 1 to 450 parts by weight, more preferably 2 to 400 parts by weight with respect to 100 parts by weight of the elastomer component. If it is less than 1 part by weight, it tends to be difficult to detect a change in the magnetic field, and if it exceeds 450 parts by weight, the magnetic elastomer itself may become brittle.
- a sealing material for sealing the polymer matrix layer 3 may be provided to the extent that the flexibility of the polymer matrix layer 3 is not impaired.
- a thermoplastic resin, a thermosetting resin, or a mixture thereof can be used as the sealing material.
- thermoplastic resin examples include styrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, polyisoprene-based thermoplastic elastomers, Fluorine-based thermoplastic elastomer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, fluororesin, polyamide, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polybutadiene Etc.
- thermosetting resin examples include polyisoprene rubber, polybutadiene rubber, styrene / butadiene rubber, polychloroprene rubber, diene-based synthetic rubber such as acrylonitrile / butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, butyl rubber, Non-diene rubbers such as acrylic rubber, polyurethane rubber, fluorine rubber, silicone rubber, epichlorohydrin rubber, natural rubber, polyurethane resin, silicone resin, epoxy resin and the like can be mentioned. These films may be laminated, or may be a film including a metal foil such as an aluminum foil or a metal vapor deposition film in which a metal is vapor deposited on the film.
- a metal foil such as an aluminum foil or a metal vapor deposition film in which a metal is vapor deposited on the film.
- the polymer matrix layer 3 may be one in which fillers are unevenly distributed in the thickness direction.
- the polymer matrix layer 3 may have a structure composed of two layers of a region on one side with a relatively large amount of filler and a region on the other side with a relatively small amount of filler.
- the region on one side containing a large amount of filler the change in the external field with respect to the small deformation of the polymer matrix layer 3 becomes large, so that the sensor sensitivity to a low internal pressure can be enhanced.
- the region on the other side with relatively little filler is relatively flexible and easy to move. By attaching this region, the polymer matrix layer 3 (especially the region on one side) is likely to be deformed.
- the filler uneven distribution ratio in the region on one side is preferably more than 50, more preferably 60 or more, and further preferably 70 or more. In this case, the filler uneven distribution rate in the other region is less than 50.
- the filler uneven distribution rate in the region on one side is 100 at the maximum, and the filler uneven distribution rate in the region on the other side is 0 at the minimum. Therefore, a laminate structure of an elastomer layer containing a filler and an elastomer layer not containing a filler may be used.
- the filler After introducing the filler into the elastomer component, it can be allowed to stand at room temperature or at a predetermined temperature, and then spontaneously settled according to the weight of the filler, by changing the temperature and time of standing.
- the filler uneven distribution rate can be adjusted.
- the filler may be unevenly distributed using a physical force such as centrifugal force or magnetic force.
- the polymer matrix layer may be constituted by a laminate composed of a plurality of layers having different filler contents.
- the filler uneven distribution rate is measured by the following method. That is, the cross section of the polymer matrix layer is observed at a magnification of 100 using a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDS). The area of the entire cross section in the thickness direction and the two areas obtained by dividing the cross section into two in the thickness direction are each subjected to elemental analysis of a metal element specific to the filler (for example, Fe element in the case of the magnetic filler of this embodiment). Find the abundance. For this abundance, the ratio of one area to the entire area in the thickness direction is calculated, and this is used as the filler uneven distribution rate in the one area. The filler uneven distribution rate in the other region is the same as this.
- SEM-EDS scanning electron microscope-energy dispersive X-ray analyzer
- the other region with relatively little filler may have a structure formed of a foam containing bubbles.
- the polymer matrix layer 3 is further easily deformed and the sensor sensitivity is enhanced.
- region of one side may be formed with the foam with the area
- Such a polymer matrix layer in which at least a part in the thickness direction is a foam is composed of a laminate composed of a plurality of layers (for example, a non-foamed layer containing a filler and a foamed layer not containing a filler). It doesn't matter.
- a magnetoresistive element for example, a magnetoresistive element, a Hall element, an inductor, an MI element, a fluxgate sensor, or the like can be used as the detection unit 4 that detects a change in the magnetic field.
- the magnetoresistive element include a semiconductor compound magnetoresistive element, an anisotropic magnetoresistive element (AMR), a giant magnetoresistive element (GMR), and a tunnel magnetoresistive element (TMR).
- AMR anisotropic magnetoresistive element
- GMR giant magnetoresistive element
- TMR tunnel magnetoresistive element
- the Hall element is preferable because it has high sensitivity over a wide range and is useful as the detection unit 4.
- the Hall element for example, EQ-430L manufactured by Asahi Kasei Electronics Corporation can be used.
- the secondary battery 2 in which the gas expansion has progressed may lead to troubles such as ignition and rupture
- charging and discharging are performed. It is configured to be blocked.
- the signal detected by the detection sensor 5 is transmitted to the control device 6, and the control device 6 transmits a signal to the switching circuit 7 when a change in the external field exceeding the set value is detected by the detection sensor 5.
- the current from the power generation device (or charging device) 8 is cut off, and charging / discharging to the battery module 1 is cut off. Thereby, the trouble resulting from gas bulging can be prevented beforehand.
- the secondary battery is a lithium ion secondary battery
- the present invention is not limited thereto.
- the secondary battery used is not limited to a non-aqueous electrolyte secondary battery such as a lithium ion battery, and may be an aqueous electrolyte secondary battery such as a nickel metal hydride battery.
- the polymer matrix layer may contain conductive fillers such as metal particles, carbon black, and carbon nanotubes as fillers, and the detector may detect changes in the electric field (changes in resistance and dielectric constant) as external fields. It is done.
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Abstract
Description
図8のグラフは、負極半電池の放電容量と電位との関係を示す曲線L7(第4曲線に相当)、および、その放電容量と変形量との関係を示す曲線L8(第3曲線に相当)を含む。負極半電池とは、負極とリチウムメタルなどの一定電位を示す電極と組み合わせた電池を指す。上述したフィッティング方法と同様の方法により、曲線L8を前記曲線L1にフィッティングする(ステップ7)。このフィッティング処理により求められる曲線(第5曲線に相当)の図示は省略する。
曲線L8を曲線L1にフィッティング処理するときに用いた充放電容量の拡大率XrとX軸方向のシフト量Xsを曲線L7に適用し、フィッティング後の負極半電池の放電容量と電位との関係を示す曲線L9(図9参照、第6曲線に相当)を取得する(ステップ8)。
前記ステップ4で取得した充放電容量Qmに対応する負極電位EAmを曲線L9に基づいて取得する(ステップ9)。
前記変形量Tmの時に取得した電池電圧Vから負極電位EAmを減ずることによって正極電位ECmを取得する(ステップ10)。
上記の方法によれば、通常の制御方法では電池電圧しか取得できなかったところ、正極と負極それぞれの電位を取得することができる。
この負極電位EAmまたは正極電位ECmが予め設定した値(正極電位の値)の範囲内となるように電池を使用することで、正極または負極での副反応を抑制することができ、これにより電池寿命を向上させることができる。
2 密閉型二次電池
3 高分子マトリックス層
4 検出部
5 検出センサ
6 制御装置
7 スイッチング回路
8 発電装置または充電装置
21 外装体
22 電極群
23 正極
24 負極
25 セパレータ
L1 第1曲線
L2 第2曲線
LS 基準曲線
Claims (16)
- 密閉型二次電池の残容量予測方法において、
残容量を予測する時点よりも前の充放電サイクルC1中に前記密閉型二次電池の変形を検出し、前記密閉型二次電池の充放電容量と変形量との関係を表す第1曲線を求めるステップと、
所定の基準状態における前記密閉型二次電池の充放電容量と変形量との関係を表す基準曲線を、前記第1曲線にフィッティング処理して第2曲線を求めるステップと、
前記充放電サイクルC1より後の充放電サイクルC2中に前記密閉型二次電池の変形量Tmを検出するステップと、
前記密閉型二次電池の変形量Tmに対応する充放電容量Qmを前記第2曲線に基づいて取得し、前記第2曲線における完全放電状態の充放電容量Qdと前記充放電容量Qmとの差を残容量として求めるステップとを備えることを特徴とする密閉型二次電池の残容量予測方法。 - 前記充放電サイクルC1が前記充放電サイクルC2の直近100サイクル以内にある請求項1に記載の密閉型二次電池の残容量予測方法。
- 前記基準曲線が、充電深度100(%)を超える満充電状態からの放電容量または充電深度100(%)を超える満充電状態までの充電容量と、前記密閉型二次電池の変形量との関係を表すものである請求項1または2に記載の密閉型二次電池の残容量予測方法。
- 前記基準曲線を前記第1曲線にフィッティング処理するときに用いた充放電容量の拡大率を、活物質の維持率として取得する請求項1~3いずれか1項に記載の密閉型二次電池の残容量予測方法。
- 前記基準曲線を前記第1曲線にフィッティング処理するときに用いた充放電容量のシフト量を、副反応による正負極の容量バランスずれ量として取得する請求項1~4いずれか1項に記載の密閉型二次電池の残容量予測方法。
- 前記密閉型二次電池に高分子マトリックス層を貼り付け、前記高分子マトリックス層は、その高分子マトリックス層の変形に応じて外場に変化を与えるフィラーを分散させて含有したものであり、
その高分子マトリックス層の変形に応じた前記外場の変化を検出することにより、前記密閉型二次電池の変形を検出する請求項1~5いずれか1項に記載の密閉型二次電池の残容量予測方法。 - 前記高分子マトリックス層が前記フィラーとしての磁性フィラーを含有し、
前記外場としての磁場の変化を検出することにより、前記密閉型二次電池の変形を検出する請求項6に記載の密閉型二次電池の残容量予測方法。 - 密閉型二次電池の残容量予測システムにおいて、
前記密閉型二次電池の変形を検出する検出センサと、前記密閉型二次電池の残容量の予測値を算出する制御装置とを備え、
前記制御装置が、
残容量を予測する時点よりも前の充放電サイクルC1中に前記密閉型二次電池の変形を検出し、前記密閉型二次電池の充放電容量と変形量との関係を表す第1曲線を求め、
所定の基準状態における前記密閉型二次電池の充放電容量と変形量との関係を表す基準曲線を、前記第1曲線にフィッティング処理して第2曲線を求め、
前記充放電サイクルC1より後の充放電サイクルC2中に前記密閉型二次電池の変形量Tmを検出し、
前記密閉型二次電池の変形量Tmに対応する充放電容量Qmを前記第2曲線に基づいて取得し、前記第2曲線における完全放電状態の充放電容量Qdと前記充放電容量Qmとの差を残容量として求めるように構成されていることを特徴とする密閉型二次電池の残容量予測システム。 - 前記充放電サイクルC1が前記充放電サイクルC2の直近100サイクル以内にある請求項8に記載の密閉型二次電池の残容量予測システム。
- 前記基準曲線が、充電深度100(%)を超える満充電状態からの放電容量または充電深度100(%)を超える満充電状態までの充電容量と、前記密閉型二次電池の変形量との関係を表すものである請求項8または9に記載の密閉型二次電池の残容量予測システム。
- 前記制御装置が、前記基準曲線を前記第1曲線にフィッティング処理するときに用いた充放電容量の拡大率を、活物質の維持率として取得可能に構成されている請求項8~10いずれか1項に記載の密閉型二次電池の残容量予測システム。
- 前記制御装置が、前記基準曲線を前記第1曲線にフィッティング処理するときに用いた充放電容量のシフト量を、副反応による正負極の容量バランスずれ量として取得可能に構成されている請求項8~11いずれか1項に記載の密閉型二次電池の残容量予測システム。
- 前記検出センサが、前記密閉型二次電池に貼り付けられる高分子マトリックス層と、検出部とを備え、
前記高分子マトリックス層が、その高分子マトリックス層の変形に応じて外場に変化を与えるフィラーを分散させて含有しており、前記検出部が前記外場の変化を検出可能に構成されている請求項8~12いずれか1項に記載の密閉型二次電池の残容量予測システム。 - 前記高分子マトリックス層が前記フィラーとしての磁性フィラーを含有しており、前記検出部が前記外場としての磁場の変化を検出可能に構成されている請求項13に記載の密閉型二次電池の残容量予測システム。
- 密閉型二次電池の電池内部情報の取得方法において、
残容量を予測する時点よりも前の充放電サイクルC1中に前記密閉型二次電池の変形を検出し、前記密閉型二次電池の充放電容量と変形量との関係を表す第1曲線を求めるステップと、
所定の基準状態における前記密閉型二次電池の充放電容量と変形量との関係を表す基準曲線を、前記第1曲線にフィッティング処理して第2曲線を求めるステップと、
前記充放電サイクルC1より後の充放電サイクルC2中に前記密閉型二次電池の変形量Tmを検出するステップと、
前記密閉型二次電池の変形量Tmに対応する充放電容量Qmを前記第2曲線に基づいて取得するステップと、
半電池より取得した負極の充放電容量Qと変形量Tとの関係を表す第3曲線および半電池より取得した負極の負極電位Eと充放電容量Qとの関係を表す第4曲線のうち、前記第3曲線を前記第1曲線にフィッティング処理して第5曲線を求めるステップと、
第4曲線の負極電位Eと充放電容量Qとの関係に、前記第3曲線を前記第1曲線にフィッティング処理するときに用いた充放電容量Qのシフト量および拡大率を適用し、第6曲線を求めるステップと、
前記密閉型二次電池の充放電容量Qmに対応する負極電位EAmを前記第6曲線に基づいて取得するステップと、電池電圧Vの値から前記負極電位EAmの値を減ずることによって正極電位ECmを取得するステップを備えることを特徴とする密閉型二次電池の電池内部情報の取得方法。 - 請求項15に記載の密閉型二次電池の電池内部情報の取得方法を使用し、
前記負極電位EAmまたは前記正極電位ECmが予め設定した前記正極電位の範囲内で電池を使用することを特徴とする電池制御方法。
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