WO2024079493A1 - 全固体電池及び全固体電池の制御方法 - Google Patents

全固体電池及び全固体電池の制御方法 Download PDF

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Publication number
WO2024079493A1
WO2024079493A1 PCT/IB2022/000579 IB2022000579W WO2024079493A1 WO 2024079493 A1 WO2024079493 A1 WO 2024079493A1 IB 2022000579 W IB2022000579 W IB 2022000579W WO 2024079493 A1 WO2024079493 A1 WO 2024079493A1
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WIPO (PCT)
Prior art keywords
battery cell
temperature
solid
battery
lithium metal
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Ceased
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PCT/IB2022/000579
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English (en)
French (fr)
Japanese (ja)
Inventor
圭司 岡田
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Renault SAS
Nissan Motor Co Ltd
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Renault SAS
Nissan Motor Co Ltd
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Priority to JP2024550915A priority Critical patent/JPWO2024079493A1/ja
Priority to PCT/IB2022/000579 priority patent/WO2024079493A1/ja
Priority to CN202280100942.XA priority patent/CN120035903A/zh
Publication of WO2024079493A1 publication Critical patent/WO2024079493A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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 an all-solid-state battery and a method for controlling an all-solid-state battery.
  • Batteries are known that are configured so that their operation is controlled according to temperature.
  • Patent Document 1 JP2013-20891A discloses an invention relating to a restraining structure for a battery pack.
  • a control unit acquires temperature information of the battery pack and compares the detected actual temperature with a pre-stored reference temperature. If the actual temperature is higher than the reference temperature, the control unit outputs a command to the restraining pressure variable device to "reduce the restraining pressure," and the restraining pressure of the restraining band is adjusted based on this command.
  • Patent Document 2 JP2002-141112A discloses a battery device that is characterized in that when a temperature sensor detects a preset temperature of the external surface or internal atmosphere of the battery storage means, the battery is discharged to a capacity that is equal to or less than a predetermined ratio of the reference capacity.
  • All-solid-state batteries are secondary batteries that use a solid electrolyte.
  • all-solid-state batteries they are particularly studying all-solid-state batteries that have a negative electrode that contains metallic lithium.
  • metallic lithium is highly reactive. Therefore, in the unlikely event that the temperature becomes abnormally high, it is desirable to prevent leakage of molten metallic lithium.
  • Patent Document 1 and Patent Document 2 do not describe an all-solid-state battery having a negative electrode containing metallic lithium. Therefore, the object of the present invention is to provide an all-solid-state battery and a control method thereof that can prevent metallic lithium from leaking to the outside even in the unlikely event that the temperature becomes abnormally high.
  • FIG. 1 is a block diagram showing a schematic configuration of an all-solid-state battery according to a first embodiment.
  • FIG. 2 is a flowchart showing a control method for the all-solid-state battery according to the first embodiment.
  • FIG. 3 is a schematic block diagram showing an all-solid-state battery according to the second embodiment.
  • FIG. 4 is a flowchart showing a control method for the all-solid-state battery according to the second embodiment.
  • FIG. 5 is a diagram showing a schematic diagram of the relationship between the control content of the all-solid-state battery, the charge amount, and the temperature of the battery cell.
  • FIG. 6 is a schematic diagram illustrating an example of a battery cell according to the second embodiment.
  • FIG. 1 is a block diagram showing a schematic configuration of an all-solid-state battery 1 according to a first embodiment.
  • the all-solid-state battery 1 according to this embodiment is, for example, a secondary battery mounted on a vehicle or the like.
  • the solid-state battery 1 includes a battery cell 2, a temperature detection mechanism 3, a restraint mechanism 4, a discharge mechanism 5, and a control mechanism 6.
  • the battery cell 2 is a part that realizes the charge and discharge function.
  • the battery cell 2 includes a solid electrolyte, a positive electrode, and a negative electrode.
  • the negative electrode contains lithium metal.
  • lithium ions move from the positive electrode to the negative electrode via the solid electrolyte, and lithium metal is precipitated on the negative electrode.
  • the lithium metal of the negative electrode moves to the positive electrode side as lithium ions and is absorbed by the positive electrode. In other words, when discharging, lithium metal is lost from the negative electrode.
  • the battery cell 2 included in the all-solid-state battery 1 may be a single cell or multiple cells.
  • the restraining mechanism 4 is configured to restrain (pressurize) the battery cell 2. To obtain the desired battery characteristics in the all-solid-state battery 1, each electrode must be firmly bonded to the solid electrolyte. Therefore, the battery cell 2 is restrained by the restraining mechanism 4 so that each electrode is firmly bonded to the solid electrolyte. When multiple battery cells 2 are provided, the multiple battery cells 2 are restrained by the restraining mechanism 4.
  • the restraining mechanism 4 is also provided for vibration resistance. That is, the restraining mechanism 4 imparts vibration resistance to the battery cell 2. For example, if the all-solid-state battery 1 is mounted on a vehicle, the vibrations of the vehicle may be applied to the battery cell 2. The vibrations may cause components contained in the battery cell 2 to disperse. If multiple battery cells 2 are provided, the vibrations may cause the multiple battery cells 2 to disperse. In contrast, because the battery cell 2 is restrained by the restraining mechanism 4, dispersion of the components is prevented even when vibrations are applied.
  • the restraint mechanism 4 is configured to allow the restraint pressure to be adjusted.
  • the specific configuration of the restraint mechanism 4 is not particularly limited.
  • the restraint mechanism 4 can be realized by a pair of end plates arranged to sandwich the battery cells 2 in the stacking direction, and an actuator configured to apply pressure to and restrain the battery cells 2 with the pair of end plates.
  • the discharge mechanism 5 is configured to discharge the battery cell 2.
  • the discharge mechanism 5 can be realized, for example, by a load circuit connected to the battery cell 2.
  • the temperature detection mechanism 3 is configured to detect the temperature of the battery cell 2 and generate temperature data. Specifically, the temperature detection mechanism 3 detects the temperature of the negative electrode of the battery cell 2.
  • the temperature detection mechanism 3 may be configured to measure the temperature of the battery cell 2 directly or indirectly. For example, the temperature detection mechanism 3 may be configured to indirectly determine the temperature of the battery cell 2 by measuring the temperature at a position somewhat distant from the battery cell 2.
  • the control mechanism 6 acquires temperature data from the temperature detection mechanism 3, and controls the operation of the all-solid-state battery 1 based on the acquired temperature data.
  • the control mechanism 6 is realized by a computer such as a microcomputer. That is, the control mechanism 6 includes a storage device such as a memory that stores a control program, and a calculation device such as a CPU that executes the control program. In the control mechanism 6, the function is realized by the calculation device executing the control program. Specifically, the control mechanism 6 is programmed to control the operation of the all-solid-state battery 1 so that molten metallic lithium does not leak, even if the battery cell 2 abnormally heats up and becomes hot.
  • FIG. 2 is a flowchart showing a method for controlling the all-solid-state battery 1 executed by the control mechanism 6. The method for controlling the all-solid-state battery 1 will be described in detail below with reference to FIG. 2.
  • Step S10 the control mechanism 6 detects the temperature of the battery cell 2. That is, the control mechanism 6 obtains temperature data from the temperature detection mechanism 3.
  • Step S20 When the temperature data is acquired, the control mechanism 6 compares the temperature of the battery cell 2 with a preset first temperature T1.
  • the first temperature T1 is a temperature that serves as a criterion for determining whether or not an abnormal temperature rise occurs.
  • the first temperature T1 is set, for example, within a range of 100 to 150°C.
  • the first temperature T1 may be, for example, a temperature at which the control mechanism 6 determines that an abnormal temperature rise occurs and notifies the user of the abnormal temperature rise via a notification mechanism such as a lamp.
  • Step S30 When the temperature of the battery cell 2 is lower than the first temperature T1, it can be said that the battery cell 2 is in a normal state. Therefore, the control mechanism 6 does not perform any particular process. That is, the all-solid-state battery 1 is operated in a normal operation.
  • Step S40 On the other hand, if the temperature of the battery cell 2 is equal to or higher than the first temperature T1, the control mechanism 6 further compares the temperature of the battery cell with a second temperature T2.
  • the second temperature T2 is a temperature higher than the first temperature T1, and is set from the viewpoint of determining whether or not the lithium metal melts.
  • the second temperature T2 is set to a value within a range of, for example, 150 to 210°C, preferably 160 to 200°C.
  • Step S50 If the temperature of the battery cell 2 is lower than the second temperature T2 in step S40, the control mechanism 6 causes the discharge mechanism 5 to discharge the battery cell 2 while causing the restraint mechanism 4 to restrain the battery cell 2 at a first restraint pressure.
  • the first confinement pressure may be of a magnitude sufficient to maintain the vibration resistance of the battery cells 2.
  • the first confinement pressure may be the same as the confinement pressure during normal operation (step S30), but may be different from that during normal operation as long as the vibration resistance is maintained. In any case, a certain level of confinement pressure is maintained, ensuring the vibration resistance of the battery cells 2.
  • the lithium metal present in the negative electrode moves to the positive electrode side and is absorbed in the positive electrode.
  • the lithium absorbed in the positive electrode does not usually melt.
  • the amount of lithium metal that can melt is reduced before the temperature of the battery cell 2 reaches the melting temperature of lithium metal.
  • Step S60 On the other hand, if the temperature of the battery cell 2 is equal to or higher than the second temperature T2 in step S40, the control mechanism 6 reduces the confinement pressure of the battery cell 2 by the confinement mechanism 4 to a second confinement pressure lower than the first confinement pressure. If the temperature of the battery cell 2 is equal to or higher than the second temperature T2, it is considered that the lithium metal is molten. If the battery cell 2 is confined with a strong force while the lithium metal is molten, the molten lithium metal is likely to leak to the outside of the battery cell 2. In contrast, by reducing the confinement pressure in this step, the lithium metal is less likely to leak to the outside even if it is molten.
  • the second confinement pressure only needs to be smaller than the confinement pressure (first confinement pressure) in step S50.
  • the second confinement pressure is substantially zero.
  • the control mechanism 6 controls the confinement mechanism 4 so that the confinement pressure of the battery cell 2 is released.
  • step 60 the control mechanism 6 does not perform the discharge operation.
  • step S3 the normal operation (step S3) is performed when the temperature of the battery cell 2 is equal to or lower than the first temperature T1.
  • the input/output of the battery cell 2 may be restricted by the control mechanism 6 when the temperature approaches the first temperature T1 to a certain extent.
  • the all-solid-state battery 1 includes a battery cell 2 having a negative electrode containing lithium metal, a restraining mechanism 4 that restrains the battery cell, a discharge mechanism 5 that discharges the battery cell 2, a temperature detection mechanism 3 that detects the temperature of the battery cell 2 and generates temperature data, and a control mechanism 6 that controls the operation of the restraining mechanism 4 and the discharge mechanism 5 based on the temperature data.
  • the control mechanism 6 restrains the battery cell 2 at a first restraining pressure by the restraining mechanism 4 while discharging the battery cell 2 by the discharge mechanism 5.
  • the control mechanism 6 is configured to reduce the restraining pressure by the restraining mechanism 4 to a second restraining pressure lower than the first restraining pressure.
  • the control method for the all-solid-state battery is a control method for an all-solid-state battery 1 including a battery cell 2 having a negative electrode containing lithium metal, and configured so that the battery cell 2 is constrained.
  • This control method includes a step of detecting the temperature of the battery cell 2 (step S10) and a step of controlling the operation of the battery cell 2 based on the temperature of the battery cell 2 (steps S50, S60).
  • the control step includes a step of discharging the battery cell 2 while constraining the battery cell 2 at a first constraining pressure (step S50) when the temperature of the battery cell 2 is equal to or higher than a preset first temperature T1 and lower than a preset second temperature T2, and a step of reducing the constraining pressure of the battery cell 2 to a second constraining pressure lower than the first constraining pressure (step S60) when the temperature of the battery cell 2 is equal to or higher than the second temperature T2.
  • the battery cell 2 when the temperature of the battery cell 2 reaches or exceeds the first temperature T1, the battery cell 2 discharges, thereby reducing the amount of lithium metal that may leak when melted in advance. Therefore, even if the temperature at which lithium metal melts is subsequently reached, leakage of lithium metal is prevented.
  • the constrained state of the battery cell 2 is maintained at the first constraining pressure.
  • vibration resistance is maintained until the lithium metal melts.
  • the confinement pressure of the battery cell 2 is reduced to the second confinement pressure.
  • the molten lithium metal is less likely to be pushed out, and leakage to the outside is prevented.
  • Second embodiment Next, a second embodiment will be described. Note that, in the second embodiment, the same configuration as in the first embodiment can be adopted, and the description will be omitted.
  • FIG. 3 is a schematic block diagram showing an all-solid-state battery 1 according to a second embodiment.
  • a charge level detection mechanism 7 is added to the first embodiment.
  • the charge amount detection mechanism 7 is configured to detect the charge amount (e.g., SOC) of the battery cell 2. Note that “detecting the charge amount” also includes detecting the charge amount by "estimating” it. For example, the charge amount detection mechanism 7 may detect the charge amount by estimating the SOC of the battery cell 2 from the voltage or the like. The charge amount detection mechanism 7 is configured to generate charge amount data indicating the detected charge amount and notify the control mechanism 6.
  • the charge amount e.g., SOC
  • the charge amount detection mechanism 7 is configured to generate charge amount data indicating the detected charge amount and notify the control mechanism 6.
  • the control mechanism 6 controls the operation of the restraint mechanism 4 and the discharge mechanism 5 by referring to the charge amount data obtained from the charge amount detection mechanism 7 in addition to the temperature data obtained from the temperature detection mechanism 3.
  • the control method of the all-solid-state battery 1 realized by the control mechanism 6 is described in detail below.
  • FIG. 4 is a flowchart showing a method for controlling the all-solid-state battery 1 according to this embodiment.
  • FIG. 5 is a diagram showing a schematic representation of the relationship between the control content of the all-solid-state battery 1, the charge amount, and the temperature of the battery cell 2. In this embodiment, the processing of steps S21 to S23 is added to the first embodiment.
  • Steps S10 to S30 are the same as those in the first embodiment. That is, in step S10, the control mechanism 6 detects the temperature of the battery cell 2 (step S10). Then, the control mechanism 6 compares the temperature of the battery cell 2 with a first temperature T1 (step S20). If the temperature of the battery cell 2 is lower than the first temperature T1, the control mechanism 6 operates the all-solid-state battery 1 in normal operation (step S30).
  • Step S21 to S22 On the other hand, when the temperature of the battery cell 2 is equal to or higher than the first temperature T1, the charge amount of the battery cell 2 is detected. That is, the control mechanism 6 acquires charge amount data via the charge amount detection mechanism 7 (step S21). Then, the control mechanism 6 compares the charge amount of the battery cell 2 with a preset first charge amount A (%) (step S22).
  • Steps S40 to S60 The operation when the charge amount of the battery cell 2 is equal to or greater than the first charge amount A is the same as steps S40 to S60 in the first embodiment. That is, the control mechanism 6 compares the temperature of the battery cell 2 with the second temperature T2 (step S40). When the temperature of the battery cell 2 is less than the second temperature T2, the control mechanism 6 causes the restraint mechanism 4 to restrain the battery cell 2 at the first restraint pressure while discharging the battery cell 2 by the discharge mechanism 5 until the battery cell 2 becomes less than the first charge amount A (step S50).
  • the control mechanism 6 causes the restraint mechanism 4 to lower the battery cell 2 to the second restraint pressure. Furthermore, the discharge operation by the discharge mechanism 5 is not performed (step S60).
  • Step S23 On the other hand, if the charge amount of the battery cell 2 is less than the first charge amount A in step S22, the control mechanism 6 controls the restraint mechanism 4 to restrain the battery cell 2 at a third restraint pressure.
  • the third restraint pressure is a pressure at which vibration resistance is maintained and is a value greater than the second restraint pressure.
  • the third restraint pressure may be the same as or different from the first restraint pressure.
  • the control mechanism 6 does not perform a discharge process.
  • the above is the control method for the all-solid-state battery 1 according to the second embodiment.
  • the operation of the all-solid-state battery 1 is controlled in the same manner as in the first embodiment. This prevents leakage of molten lithium metal in the same manner as in the first embodiment.
  • the battery cell 2 when the charge amount of the battery cell 2 is low (i.e., when it is less than the first charge amount A), the battery cell 2 is not discharged even if the temperature of the battery cell 2 is equal to or higher than the first temperature T1 (step S23). Therefore, a certain amount of power is secured.
  • the charge amount when the all-solid-state battery 1 is mounted on a vehicle, if the discharge process is performed during an abnormal temperature rise and the power of the battery cell 2 is completely lost, the power required for evacuation of the vehicle, etc. may not be secured.
  • the charge amount when the charge amount is less than the first charge amount A, the discharge process is not performed, so a certain amount of power is secured for evacuation of the vehicle, etc. Note that when the charge amount of the battery cell 2 is low, the amount of lithium metal that can melt is small, so even if the temperature of the battery cell 2 subsequently reaches the melting temperature of lithium metal, there is little possibility that lithium metal will leak.
  • the battery cell 2 when the charge level of the battery cell 2 is less than the first charge level A, the battery cell 2 is constrained at a confinement pressure (third confinement pressure) that ensures vibration resistance even if the second temperature T2 is exceeded.
  • a confinement pressure third confinement pressure
  • the charge level of the battery cell 2 when the charge level of the battery cell 2 is less than the first charge level A, it can be said that there is little lithium metal that can melt. Therefore, even if the battery cell 2 is constrained, there is a low possibility that lithium metal will leak to the outside. Under conditions where the possibility of leakage is low, the battery cell 2 is constrained at the third constraining pressure, and vibration resistance is ensured.
  • the first charge amount A is set to a value that prevents the amount of lithium metal contained in the negative electrode from leaking to the outside. This point will be explained in detail below.
  • FIG. 6 is a schematic diagram showing an example of a battery cell 2 according to this embodiment.
  • This battery cell 2 is housed in a film-like exterior body 8. Inside the exterior body 8, a buffer space 9 is provided between the exterior body 8 and the battery cell 2. With this configuration, even if some lithium metal melts, the molten lithium metal is contained in the buffer space 9 and does not reach the outside of the exterior body 8.
  • the amount of lithium metal that can melt changes depending on the charge/discharge state of the battery cell 2. Specifically, the amount of lithium metal contained in the negative electrode increases during charging, and decreases during discharging. Therefore, the first charge amount A is set so that the amount of lithium metal contained in the negative electrode is an amount that can be accommodated in the buffer space 9. If the first charge amount A is set to such a value, when the temperature of the battery cell 2 increases abnormally (exceeds the first temperature T1), the charge amount of the battery cell 2 is reduced so that the amount of lithium metal contained in the negative electrode is within the range that can be accommodated in the buffer space 9. Therefore, even if the temperature subsequently reaches a temperature at which lithium metal melts, the molten lithium metal can be accommodated in the buffer space 9, and leakage to the outside can be prevented.
  • the first charge amount A is set to the maximum charge amount that allows the amount of lithium metal deposited on the negative electrode to be accommodated in the buffer space 9. If the first charge amount A is set to such a value, vibration resistance is maintained to the maximum extent possible as long as the amount of lithium metal in the negative electrode is an amount that can be accommodated in the buffer space 9. Furthermore, power can be used up to the temperature at which lithium metal melts (second temperature T2).

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PCT/IB2022/000579 2022-10-12 2022-10-12 全固体電池及び全固体電池の制御方法 Ceased WO2024079493A1 (ja)

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JP2024550915A JPWO2024079493A1 (https=) 2022-10-12 2022-10-12
PCT/IB2022/000579 WO2024079493A1 (ja) 2022-10-12 2022-10-12 全固体電池及び全固体電池の制御方法
CN202280100942.XA CN120035903A (zh) 2022-10-12 2022-10-12 全固态电池以及全固态电池的控制方法

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Cited By (1)

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WO2026031514A1 (zh) * 2024-08-06 2026-02-12 比亚迪股份有限公司 固态电池压力控制方法、设备、介质、车辆及装置

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JP2007087759A (ja) * 2005-09-21 2007-04-05 Nissan Motor Co Ltd ゲル電解質電池、電池ユニット、および電池用ゲル電解質層の製造方法
JP2008147010A (ja) * 2006-12-08 2008-06-26 Nissan Motor Co Ltd 電力供給装置およびその制御方法
JP2010205479A (ja) * 2009-03-02 2010-09-16 Toyota Motor Corp 圧粉全固体電池
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JP2022163356A (ja) * 2021-04-14 2022-10-26 株式会社Subaru 全固体電池制御システム

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JP2002141112A (ja) * 2000-11-06 2002-05-17 Japan Storage Battery Co Ltd 電池装置
JP7059828B2 (ja) * 2017-11-30 2022-04-26 三菱ケミカル株式会社 仕切り部材、組電池及び組電池の熱伝達制御方法

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JP2007087759A (ja) * 2005-09-21 2007-04-05 Nissan Motor Co Ltd ゲル電解質電池、電池ユニット、および電池用ゲル電解質層の製造方法
JP2008147010A (ja) * 2006-12-08 2008-06-26 Nissan Motor Co Ltd 電力供給装置およびその制御方法
JP2010205479A (ja) * 2009-03-02 2010-09-16 Toyota Motor Corp 圧粉全固体電池
JP2013017354A (ja) * 2011-07-06 2013-01-24 Clarion Co Ltd バッテリーパック
JP2022062537A (ja) * 2020-10-08 2022-04-20 日産自動車株式会社 全固体二次電池、全固体二次電池システム制御方法及び全固体二次電池システム制御装置
WO2022163539A1 (ja) * 2021-01-29 2022-08-04 パナソニックＩｐマネジメント株式会社 二次電池の充電方法および充電システム
JP2022163356A (ja) * 2021-04-14 2022-10-26 株式会社Subaru 全固体電池制御システム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026031514A1 (zh) * 2024-08-06 2026-02-12 比亚迪股份有限公司 固态电池压力控制方法、设备、介质、车辆及装置

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