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WO1998032186A1 - Module de piles sodium-soufre - Google Patents

Module de piles sodium-soufre Download PDF

Info

Publication number
WO1998032186A1
WO1998032186A1 PCT/JP1997/000061 JP9700061W WO9832186A1 WO 1998032186 A1 WO1998032186 A1 WO 1998032186A1 JP 9700061 W JP9700061 W JP 9700061W WO 9832186 A1 WO9832186 A1 WO 9832186A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
module
liquid
sulfur
sulfur battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1997/000061
Other languages
English (en)
Japanese (ja)
Inventor
Takeshi Hiranuma
Hiromi Tokoi
Naohisa Watahiki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to PCT/JP1997/000061 priority Critical patent/WO1998032186A1/fr
Publication of WO1998032186A1 publication Critical patent/WO1998032186A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • H01M10/3909—Sodium-sulfur cells
    • 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

  • a conventional natural sulfur battery module battery is composed of a plurality of unit cells 1 assembled in an insulated container 4, and sand or ceramic particles are interposed between the unit cells 1.
  • sand or ceramic particles are interposed between the unit cells 1.
  • the thirteenth goal of this study is to provide a highly reliable and safe module for sodium sulfur batteries.
  • the i! JJ module is filled with a liquid that is non-reactive with sodium and sulfur and electrically insulating between cells, and leaks sodium, sulfur, and polysulfide in the liquid.
  • Riumu is provided with a device for collecting the active material, such as c further, the module, which was provided with a control device for sensors and control them for detecting damage a pump for circulating the liquid Confuse.
  • the active material leaked from the cell and released into the surrounding liquid can be removed, and a short circuit of the adjacent battery can be prevented, the operation of the module can be continued.
  • the leaked active material can be effectively collected in the recovery device by flowing the liquid by the pump, and the damaged portion can be gradually heated to suppress the temperature change of the adjacent battery.
  • the uniformity between the batteries can be achieved, the characteristics and temperature of the batteries are stabilized, and the cells are less likely to be damaged.
  • FIG. 1 is a diagram showing a main part structure of a first embodiment of the present invention
  • FIG. 2 is a diagram showing a main part structure of a second embodiment of the present invention
  • FIG. Implementation of FIG. 4 is a view showing a main part structure of an example
  • FIG. 4 is a view showing a main part structure of a fourth embodiment of the present invention
  • FIG. 5 is a view showing one embodiment of the active material recovery apparatus of the present invention
  • FIG. The figure shows the battery operation control method based on the damage detection of the present invention.
  • FIG. 7 shows the first embodiment of the unit cell of the present invention and the position of the damage detection sensor.
  • FIG. 8 shows the unit of the present invention.
  • FIG. 7 shows the first embodiment of the unit cell of the present invention and the position of the damage detection sensor.
  • FIG. 9 is a diagram showing a second embodiment of the battery and the position of the damage detection sensor
  • FIG. 9 is a diagram showing the main structure of the first embodiment of the power storage system according to the present invention
  • FIG. FIG. 11 is a diagram showing a main part of the second embodiment of the power storage system according to the present invention
  • FIG. 11 is a diagram showing an embodiment of the active material recovery device of the present invention
  • FIG. FIG. 13 is a view showing a transportation method
  • FIG. 13 is a view showing a structure of a conventional example.
  • FIG. 1 is a diagram showing a first embodiment of the present invention.
  • the cells 1 are collectively arranged in a heat insulating container 4.
  • an electrically insulating liquid 3 that does not react with sodium and sulfur (for example, a perfluoropolyether-based heating medium, an alkylbiphenyl-based heating medium, a dibenzyltoluene-based heating medium, etc.)
  • the space is filled with inert gas 4 at the top to alleviate the expansion of the liquid.
  • An active material recovery device 5 for removing sodium, sulfur and sodium polysulfide from the liquid 3 is provided in a pipe 7 to which a pump 8 is connected.
  • the installation position of the active material recovery device 5 is not limited to the piping, but may be in an insulated container or the like as long as the active material leaked from the unit cell can be captured.
  • a leak sensor 6 for detecting the active material leaked from the cell is installed, and the active material recovery device 5 and the pump 8 are controlled by the control device 10 based on a leak signal of the leak sensor 16.
  • Ko Control The active material recovery device 5, the pump 8, the leak sensor 6, and the control device 10 are connected by a signal line 9.
  • the leakage sensor 6 changes the electrical resistance when sodium or sodium polysulfide leaks into the liquid 3.
  • Another method that detects battery damage from the electrical changes in the sodium-conducting solid conductive solid electrolyte is c.
  • Another method is to detect leakage from the rise in temperature of the liquid 3 due to the heat of reaction at the time of breakage and the acoustic change associated with the damage. Detect.
  • the active material is activated the pump 8 at that time t to remove the active material leads to the active material recovery device 5, by forced convection of the liquid 3, the reaction heat at failure is also removed.
  • the module of the present invention can continue to operate.
  • the pump 8 is always operated at the base to be used as an emergency power supply or as a power demand peak cut power supply, so that the inside of the battery is evenly heated and damage is prevented.
  • FIG. 2 is a diagram showing a second embodiment of the present invention.
  • a heating or cooling device 10 is provided in the embodiment of FIG. 1 to actively control the temperature of the liquid 3.
  • the temperature of the unit cell is kept constant, the battery performance is further stabilized, and damage is less likely to occur.
  • FIG. 3 is a view showing a third embodiment of the present invention.
  • the embodiment shown in Fig. 1 is provided with a heat storage tank 11 (which also reduces the expansion of liquid in this example), and supplies heat to an external heat load 12 or an adjacent module. is there. Joule heat generated during discharging and charging can be stored and used effectively, such as maintaining the temperature during standby and supplying heat to adjacent modules and external heat loads.
  • Figure 4 shows a fourth embodiment of the present invention.
  • the liquid 3 in the insulated container 2 is directly heated or cooled by the heating device or cooling device 1 1, and the liquid 4 is circulated using the natural convection of the liquid, eliminating the need for a pump. Become.
  • 11 is a cooling device, a downward flow of the liquid 3 occurs between the heat insulating container 2 and the partition plate 14 and an upward flow occurs between the cells, so that the cells can be cooled.
  • 11 is a heating device, an ascending flow of the liquid 3 occurs between the heat insulating container 2 and the partition plate 14, and a descending flow occurs between the cells, so that the cells can be heated.
  • FIG. 5 is a view showing a fifth embodiment of the present invention.
  • the liquid 3 in the heat insulating container 2 is replaced with the liquid 3 in the heat storage tank 12. This prevents the damage from spreading and allows the battery to continue operating, as in Example 1.
  • FIG. 6 is a diagram showing a specific example of a control method of the present invention. If damage is detected, activate the active material recovery device and pump. However, if the damage is still widespread, for example when the temperature continues to rise or the electrical resistance of the liquid continues to drop, the battery output is temporarily reduced to prevent the damage from spreading.
  • FIG. 7 is a view showing a specific example of the arrangement of the unit cell and the leak sensor of the present invention.
  • Sodium is lighter than liquid, and the temperature rises due to the heat generated due to breakage, and the density becomes lighter and the liquid rises, so the leak sensor that detects electrical resistance, Na leak, and temperature is installed above the cell. By doing so, leakage can be detected with a small number of sensors.
  • the separators 14 between the collections of the cells 1 connected to the terminals 15 in series are connected in parallel to the collection of batteries including the damaged batteries in series. This prevents the active material from leaking and accumulates in the collection of batteries, and reduces the effect of reduced output due to damaged batteries to only the stains of series batteries including damaged batteries.
  • FIG. 8 is a view showing a second specific example of the arrangement of the unit cell and the leak sensor according to the present invention. If a liquid is flowing during power generation, a leak sensor that detects electrical resistance, Na leak, and temperature is installed downstream. Liquid flows Therefore, if damage occurs on the upstream side, an increase in electrical resistance, temperature, Na leakage, etc. can be detected on the downstream side, so the number of upstream leakage sensors can be reduced.
  • FIG. 9 is a diagram showing a specific example of the power storage system of the present invention.
  • FIG. 11 is a view showing a specific example of the active material recovery device of the present invention. Sodium 18, sulfur 19, and sodium polysulfide 20 leaked from the pipe 7 are mixed with the liquid 3 and flow.
  • liquid 3 is, for example, a perfluoropolyether-based heating medium
  • the density at the battery operating temperature is about 1.3 g
  • the density of sulfur 15 is about 1.7 g. 5 precipitates and accumulates in the sulfur recovery tank 24 at the bottom of the active material recovery device.
  • Sodium 14 and sulfur 15 can be discharged from the drain valve 22.
  • FIG. 12 is a view showing a transportation method of the present invention. After transporting the battery from the battery manufacturing site to the battery installation location, filling it with liquid reduces the volume required for transportation. Can be
  • the present invention can provide a highly reliable and safe module of one sodium sulfur pond as in the above embodiment. Industrial applicability
  • the active material leaked from the cell and released into the surrounding liquid can be removed, a short circuit between adjacent cells can be prevented, and the module can be operated continuously.
  • the leaked material can be effectively collected in the recovery device by flowing the liquid by the pump, and the temperature of the adjacent battery can be suppressed by gradually heating the damaged portion.
  • the temperature between the batteries can be made uniform or constant by applying liquid heat or gradual heating, the characteristics and temperature of the entire battery are stabilized, and the battery is less likely to be damaged.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

Module de piles sodium-soufre qui comporte des piles (1) séparées par des espaces remplis d'un liquide isolant (3) qui ne réagit ni avec le sodium, ni avec le soufre. Un dispositif de récupération (5) empêche le court circuit entre des piles adjacentes en récupérant une matière active, telle que du sodium ou du soufre ayant fui dans le liquide, ou du polysulfure de sodium, etc. et prélève la chaleur des piles ou égalise les températures de piles adjacentes en faisant circuler le liquide. Par conséquent, ledit module peut fonctionner en continu, même lorsque certaines des piles sont en panne et, en même temps, les piles sont protégées contre les dommages par la stabilisation de leurs caractéristiques et de leur température.
PCT/JP1997/000061 1997-01-16 1997-01-16 Module de piles sodium-soufre Ceased WO1998032186A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP1997/000061 WO1998032186A1 (fr) 1997-01-16 1997-01-16 Module de piles sodium-soufre

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1997/000061 WO1998032186A1 (fr) 1997-01-16 1997-01-16 Module de piles sodium-soufre

Publications (1)

Publication Number Publication Date
WO1998032186A1 true WO1998032186A1 (fr) 1998-07-23

Family

ID=14179919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/000061 Ceased WO1998032186A1 (fr) 1997-01-16 1997-01-16 Module de piles sodium-soufre

Country Status (1)

Country Link
WO (1) WO1998032186A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112008001675T5 (de) 2007-06-29 2010-08-05 Toyota Jidosha Kabushiki Kaisha, Toyota-shi Leistungsspeichervorrichtung
US8298694B2 (en) 2007-02-01 2012-10-30 Toyota Jidosha Kabushiki Kaisha Power supply device
WO2013187096A1 (fr) * 2012-06-15 2013-12-19 日本碍子株式会社 Récipient isolant pour batterie, dispositif de commande de batterie, et procédé de détection de défaillance de batterie
KR20140022687A (ko) * 2012-08-14 2014-02-25 재단법인 포항산업과학연구원 나트륨 유황 전지
JP2017502450A (ja) * 2013-10-30 2017-01-19 シーメンス アクティエンゲゼルシャフト 高温バッテリーを備えた熱貯蔵システム
WO2025094536A1 (fr) * 2023-11-02 2025-05-08 三菱自動車工業株式会社 Dispositif de refroidissement pour bloc-batterie

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63202865A (ja) * 1987-02-18 1988-08-22 Hitachi Ltd ナトリウム−硫黄電池システム
JPH03203169A (ja) * 1989-12-29 1991-09-04 Ngk Insulators Ltd 高温電池装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63202865A (ja) * 1987-02-18 1988-08-22 Hitachi Ltd ナトリウム−硫黄電池システム
JPH03203169A (ja) * 1989-12-29 1991-09-04 Ngk Insulators Ltd 高温電池装置

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8298694B2 (en) 2007-02-01 2012-10-30 Toyota Jidosha Kabushiki Kaisha Power supply device
DE112008001675T5 (de) 2007-06-29 2010-08-05 Toyota Jidosha Kabushiki Kaisha, Toyota-shi Leistungsspeichervorrichtung
US8349481B2 (en) 2007-06-29 2013-01-08 Toyota Jidosha Kabushiki Kaisha Power storage apparatus
WO2013187096A1 (fr) * 2012-06-15 2013-12-19 日本碍子株式会社 Récipient isolant pour batterie, dispositif de commande de batterie, et procédé de détection de défaillance de batterie
US10147976B2 (en) 2012-06-15 2018-12-04 Ngk Insulators, Ltd. Insulating container for battery, battery control device, and battery-failure detection method
KR20140022687A (ko) * 2012-08-14 2014-02-25 재단법인 포항산업과학연구원 나트륨 유황 전지
JP2017502450A (ja) * 2013-10-30 2017-01-19 シーメンス アクティエンゲゼルシャフト 高温バッテリーを備えた熱貯蔵システム
WO2025094536A1 (fr) * 2023-11-02 2025-05-08 三菱自動車工業株式会社 Dispositif de refroidissement pour bloc-batterie

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