WO2015008341A1 - Module de batterie secondaire et système de batterie - Google Patents

Module de batterie secondaire et système de batterie Download PDF

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Publication number
WO2015008341A1
WO2015008341A1 PCT/JP2013/069338 JP2013069338W WO2015008341A1 WO 2015008341 A1 WO2015008341 A1 WO 2015008341A1 JP 2013069338 W JP2013069338 W JP 2013069338W WO 2015008341 A1 WO2015008341 A1 WO 2015008341A1
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WO
WIPO (PCT)
Prior art keywords
battery
battery module
gas
container
exhaust valve
Prior art date
Application number
PCT/JP2013/069338
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English (en)
Japanese (ja)
Inventor
日高　貴志夫
Original Assignee
株式会社 日立製作所
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 株式会社 日立製作所 filed Critical 株式会社 日立製作所
Priority to PCT/JP2013/069338 priority Critical patent/WO2015008341A1/fr
Publication of WO2015008341A1 publication Critical patent/WO2015008341A1/fr

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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
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • 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
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/394—Gas-pervious parts or elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a secondary battery module and a battery system.
  • Patent Document 1 JP 2012-99432 discloses a battery and a battery module in which a sheet battery is wound and stored in a can. When the inside of the container becomes high pressure due to the gas generated during charging / discharging of the lithium ion secondary battery, the gas is discharged to the outside by a valve attached to the container to prevent pressurization.
  • Patent Document 2 JP 2007-200717 (Patent Document 2) includes a space for holding the generated gas in advance around the laminate battery, and a structure for holding the generated gas when the gas is generated.
  • Patent Document 3 JP-A-2005-332726 (Patent Document 3) includes a space for holding the generated gas in advance around the laminate battery and a gas discharge portion.
  • Patent Document 4 JP-A-2003-168410 (Patent Document 4) includes a case for storing a laminated battery. When the amount exceeds a certain amount, gas is released by a protrusion provided on the inner wall of the case.
  • JP 2012-99432 A JP2007-200717A JP2005-332726 JP 2003-168410 A
  • Gas generation is caused by vaporization or decomposition of the non-aqueous electrolyte under abnormal conditions such as high temperatures.
  • the pressurization prevention valve is broken, it is opened to the outside, so that the atmosphere containing moisture enters the inside of the can after the gas release, and is restored to the atmosphere inside the can before the gas release. do not do.
  • a battery member is exposed to the atmosphere, a chemical reaction that deteriorates battery characteristics proceeds, and battery performance cannot be maintained.
  • Patent Documents 2 to 4 as in Patent Document 1, when the pressure inside the container becomes high, the laminate opens and the inside of the laminate becomes atmospheric pressure, so that air flows into the laminate from the opening. As the battery material deteriorates, the battery performance decreases rapidly.
  • an object of the present invention is to provide a secondary battery module capable of maintaining battery performance for a certain period even if the generated gas is released.
  • the laminate battery has a structure in which an electrode group including a positive electrode and a negative electrode and a separator disposed between the positive electrode and the negative electrode is covered with a laminate material filled with a non-aqueous electrolyte.
  • a feature of the present invention that solves the above-described problems is characterized in that one or a plurality of laminated batteries and a battery container covering the laminated batteries are provided, and a differential exhaust valve is provided in the battery container. Moreover, it is preferable that the inside of a battery container is pressure-reduced compared with external atmospheric pressure.
  • HEV vehicles hybrid vehicles
  • EV vehicles electric vehicles powered by motors
  • PHV vehicle plug-in hybrid vehicle
  • the battery In order to satisfy the requirements for driving a motor mounted on an automobile, it is necessary to increase the battery power density, extend the service life, and provide high reliability for safety. In addition, a charging speed comparable to the fueling speed of a gasoline automobile is also an issue. Therefore, the battery is required to have good response characteristics with respect to charging / discharging using a large current and resistance in harsh environments such as ultra-high temperatures and extremely low temperatures.
  • a laminate type battery is used as a battery mounted on an automobile. Used in harsh environments with high temperatures and high currents such as rapid charge and discharge, and when it deteriorates, it involves gas generation due to decomposition of the electrolyte, and thus the laminate type battery tends to swell. As a result, the deterioration further proceeds due to expansion and rupture of the laminated battery. By realizing pressure reduction in the battery, it is possible to prevent the battery from being deteriorated in a harsh environment and improve safety.
  • the present inventors effectively prevented an increase in gas pressure in the battery and expansion of the laminate type battery by providing a vacuum container that prevents the release of gas during the driving of the battery.
  • a battery container that covers the laminated battery and a differential exhaust valve that connects the battery container and the outside are provided to store and hold the gas generated in the battery in the battery container and prevent the electrolyte gas from diffusing. Further, when the pressure exceeds a certain pressure, the suction is guided to the outside through a differential exhaust valve. As a result, the expansion of the laminate type battery is suppressed and the battery performance is maintained. In addition, when a crack occurs in the laminate seal portion and gas is released to the outside, the battery life is usually rapidly reduced.
  • the differential exhaust valve blocks the atmosphere inside the container and the atmosphere of the external environment, can prevent contact with the atmosphere even after gas is released, and can suppress deterioration of the battery. Therefore, even when the battery deteriorates during use in a harsh environment, the power supply does not stop suddenly, and the battery performance gradually deteriorates. The possibility of causing a system failure due to insufficient power supply can be reduced, which is preferable.
  • the internal pressure of the battery can be made lower than before. Furthermore, even in a battery module using a plurality of cells, the internal pressure of different batteries is maintained uniformly, contributing to performance improvement.
  • the generated gas is accumulated in the battery container, by analyzing the generated gas to the outside, it is possible to perform a gas analysis of the decomposition product of the electrolytic solution during operation. Moreover, it is also preferable to use it as a test battery for directly monitoring the deterioration behavior of high temperature and large current application.
  • 1 and 2 are schematic views of the battery of this example.
  • the laminated battery fixing plate 12 and the leaf spring 13 are pressed from both sides and held in the battery container 15 together with the gas adsorbent 14 that adsorbs the flammable gas.
  • the fixed plate 12 is arranged in parallel to both side walls of the battery container 15 and is in contact with the inner wall of the container through the leaf spring 13.
  • the plate 12 causes the laminated battery 11 to be moved from both sides by the elastic stress generated by the leaf spring 13. Hold.
  • the adsorbent 14 is exemplified by activated carbon or activated alumina.
  • the adsorbent 14 is disposed at a position such as the bottom of the container that does not contact the laminate battery 11 before expansion.
  • the upper cover 20 of the battery case 15 is provided with a differential exhaust valve 16 for depressurizing the inside of the battery case at the center, and electrode terminals 17 are attached side by side on both sides thereof.
  • the electrode terminal 17 is connected to a lead electrode drawn out from the laminated battery 11 to the outside.
  • the upper lid 20 is sealed together with the battery container 15, and the air inside the container 15 is forcibly exhausted from the differential exhaust valve 16 using a vacuum pump to be in a decompressed state. With such a configuration, the expansion of the laminated battery 11 is suppressed.
  • the laminate battery 11 has a shape in which an electrode group consisting of a positive electrode, a negative electrode, and a separator disposed between the positive and negative electrodes is covered with a laminate material and filled with an electrolytic solution containing a non-aqueous organic solvent.
  • a method for manufacturing a laminated battery will be described using a lithium ion secondary battery as an example.
  • the method for producing the positive electrode plate is as follows.
  • a positive electrode active material capable of occluding and releasing lithium ions is mixed with a conductive material such as carbon material powder and a binder such as polyvinylidene fluoride (PVDF) to prepare a slurry of an electrode mixture.
  • a conductive material such as carbon material powder
  • a binder such as polyvinylidene fluoride (PVDF)
  • PVDF polyvinylidene fluoride
  • Sufficient kneading is performed using a mixer equipped with a stirring means such as a rotor blade so that the powder particles of the positive electrode active material are uniformly dispersed in the slurry.
  • the mixing ratio of the conductive material to the positive electrode active material is preferably 5 to 20 wt%.
  • the well mixed electrode mixture slurry is applied on both sides of a current collector foil (aluminum foil having a thickness of 15 to 25 ⁇ m, etc.) using a roll transfer type coating machine or the like, and press-dried to obtain a positive electrode plate.
  • the thickness of the electrode mixture layer formed on the current collector foil is preferably 50 to 250 ⁇ m.
  • the method for producing the negative electrode plate is as follows. Using a carbon material such as graphite, amorphous carbon, or a mixture thereof as a negative electrode active material, mixing with a binder, forming a slurry similar to the positive electrode, and collecting foil (a copper foil having a thickness of 7 to 20 ⁇ m, etc.) A negative electrode plate is prepared by coating and pressing the upper part.
  • the mixing ratio of the binder to the positive electrode active material is preferably about 10 wt%. If the binder component is increased, the internal resistance value is increased. If the binder component is too small, the storage life and cycle life of the battery may be decreased.
  • the electrode mixture thickness is preferably 50 to 200 ⁇ m.
  • the tab portion is made of a metal foil made of the same material as the current collector having a rectangular shape. In a battery that requires a large current to flow, such as a lithium secondary battery for moving bodies, it is preferable to provide a plurality of tabs.
  • a tabbed electrode is stacked with a separator sandwiched between them, and a wound product, or an electrode and a separator stacked alternately, is stored as an electrode group in a covering material made of a laminate material.
  • a separator porous polyethylene (PE) resin, polypropylene (PP) resin, or the like can be used.
  • an electrolytic solution is injected and sealed.
  • the electrolytic solution it is desirable to use a solution in which LiBF 4 is dissolved as an electrolyte in a solvent such as ethylene carbonate (EC), propylene carbonate (PC), or dimethyl carbonate (DMC).
  • the electrolyte concentration is preferably between 0.6M and 1.5M.
  • FIG. 3 is a diagram showing a detailed mechanism of the differential exhaust valve 16 having a differential exhaust mechanism.
  • a circular hole is formed in the upper lid 20 of the container 15, an O-ring 22 closely attached to the periphery of the hole is installed, and a conical valve 21 larger than the diameter of the O-ring 22 is closely attached to the periphery of the O-ring 22.
  • the conical valve 21 is pressed by elastic stress.
  • a coil spring 25 for preventing air mixing at the time of evacuation and gas discharge is placed outside the column 23 on the conical valve 21, and a disk-shaped column holding plate 24 is attached on the column 23.
  • the differential exhaust valve 16 is driven via the leaf spring 26 to realize decompression inside the container 15.
  • FIG. 4 is a diagram showing the structure of the differential exhaust valve 16 and the electrode terminal 34.
  • the electrode terminal 34 is connected to a lead electrode 33 drawn from the laminate battery 11.
  • the atmosphere is shielded by the hermetic seal 35 around the lead hole provided in the upper lid 20.
  • An exhaust nozzle 32 is connected to the differential exhaust valve 16, and the pressure is reduced using a vacuum pump or the like when the internal pressure of the battery module is reduced.
  • the expansion is restrained by restraining from both sides, and the performance deterioration due to the battery swelling is prevented.
  • the generated gas is prevented from being dispersed by the vacuum atmosphere of the battery container and the flammable gas adsorbent, and the generation of flame due to gas diffusion is suppressed.
  • the internal pressure is adjusted by the operating exhaust valve, and the container rupture due to the gas pressure rise can be avoided.
  • the differential exhaust valve releases the pressurized gas to the outside of the container and immediately closes the valve, so that the entry of the atmosphere can be prevented. Contact between the battery component and the atmosphere can be prevented.
  • a gas sensor that senses the gas exhausted outside the differential exhaust valve may be provided.
  • the control circuit connected to the gas sensor detects the gas release from the battery, performs emergency evacuation control of the battery charge / discharge, and displays With the circuit and element for the above, it is possible to notify the driver of an EV vehicle or the like that a battery abnormality has occurred.
  • This example describes the configuration of a battery system that uses the battery module of Example 1 and performs battery life management.
  • FIG. 5 is a schematic diagram showing an example of the life management recording system of the present embodiment.
  • a pressure sensor 51 disposed in the battery module
  • a recording device 52 for recording or displaying a signal obtained from the pressure sensor
  • a display device 53 for displaying a signal obtained from the pressure sensor
  • a control device 54 is provided.
  • FIG. 5 is an example in which the exhaust gas passage 55 is connected to the connecting hose 56, and the exhaust valve 57 is opened and closed by the control device 54. Exhaust gas or circulating air flows in the direction of the arrow.
  • a pipe with a partly larger inner diameter on the exhaust gas flow path side is provided, and a pipe structure is formed that can take in outside air during travel from the front and compress it, and then expand and decompress it.
  • the inside of the battery container can be exhausted through the differential exhaust valve while traveling.
  • FIG. 6 is a flowchart for explaining a method of recording the opening / closing of the exhaust valve and the operation history performed by the control device.
  • the exhaust valve After starting operation, it is determined whether or not the internal pressure obtained from the pressure sensor exceeds a predetermined value (P0), and if it exceeds, the exhaust valve is operated, the differential valve is opened, and the internal pressure is decreased. Record the pressure before changing the internal pressure and the time the differential valve was operated. Again, it is determined whether or not the internal pressure obtained from the pressure sensor exceeds a predetermined value (P0). If the internal pressure is less than the predetermined value, the differential valve is closed and the internal pressure and time are recorded.
  • the recorded internal pressure and differential valve opening information is recorded in the recording device as an operation history, and is used for battery life management, prediction, device operation, and the like. In particular, the system is effective for managing battery life. It is also possible to display information such as the differential valve opening, internal pressure, and time on a display device and notify the driver or the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Gas Exhaust Devices For Batteries (AREA)

Abstract

Selon la présente invention, une batterie stratifiée possède une structure dans laquelle un groupe d'électrodes est revêtu avec un matériau de stratifié rempli avec un électrolyte non aqueux, ledit groupe d'électrodes comportant une électrode positive, une électrode négative et un séparateur qui est disposé entre l'électrode positive et l'électrode négative. La présente invention est caractérisée par le fait qu'elle comporte une ou une pluralité des batteries stratifiées et un conteneur de batterie qui recouvre les batteries stratifiées, ledit conteneur de batterie comportant une vanne d'échappement différentielle. En outre, l'intérieur du conteneur de batterie est de préférence mis en dépression en comparaison avec une pression atmosphérique extérieure. L'invention porte sur un module de batterie secondaire, dans lequel une détérioration rapide de performances est supprimée même dans les cas où un gaz est généré en provenance des batteries, et les performances de batterie peuvent être maintenues pendant une période de temps prédéterminée.
PCT/JP2013/069338 2013-07-17 2013-07-17 Module de batterie secondaire et système de batterie WO2015008341A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/069338 WO2015008341A1 (fr) 2013-07-17 2013-07-17 Module de batterie secondaire et système de batterie

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/069338 WO2015008341A1 (fr) 2013-07-17 2013-07-17 Module de batterie secondaire et système de batterie

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019096520A (ja) * 2017-11-24 2019-06-20 トヨタ自動車株式会社 リリーフ弁付き電池

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006252960A (ja) * 2005-03-10 2006-09-21 Nissan Motor Co Ltd 組電池
JP2006260975A (ja) * 2005-03-17 2006-09-28 Dainippon Printing Co Ltd 電池モジュール
JP2007273149A (ja) * 2006-03-30 2007-10-18 Dainippon Printing Co Ltd 電池モジュール
JP2007335309A (ja) * 2006-06-16 2007-12-27 Toshiba Battery Co Ltd 電池パック
JP2009187889A (ja) * 2008-02-08 2009-08-20 Nissan Motor Co Ltd 電池ケース及び組電池
JP2012252902A (ja) * 2011-06-03 2012-12-20 Hitachi Maxell Energy Ltd 非水電解質電池モジュール

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006252960A (ja) * 2005-03-10 2006-09-21 Nissan Motor Co Ltd 組電池
JP2006260975A (ja) * 2005-03-17 2006-09-28 Dainippon Printing Co Ltd 電池モジュール
JP2007273149A (ja) * 2006-03-30 2007-10-18 Dainippon Printing Co Ltd 電池モジュール
JP2007335309A (ja) * 2006-06-16 2007-12-27 Toshiba Battery Co Ltd 電池パック
JP2009187889A (ja) * 2008-02-08 2009-08-20 Nissan Motor Co Ltd 電池ケース及び組電池
JP2012252902A (ja) * 2011-06-03 2012-12-20 Hitachi Maxell Energy Ltd 非水電解質電池モジュール

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019096520A (ja) * 2017-11-24 2019-06-20 トヨタ自動車株式会社 リリーフ弁付き電池

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