US20120164490A1 - Battery module - Google Patents
Battery module Download PDFInfo
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- US20120164490A1 US20120164490A1 US13/394,272 US201013394272A US2012164490A1 US 20120164490 A1 US20120164490 A1 US 20120164490A1 US 201013394272 A US201013394272 A US 201013394272A US 2012164490 A1 US2012164490 A1 US 2012164490A1
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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
- 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
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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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
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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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/64—Heating or cooling; Temperature control characterised by the shape of the cells
- H01M10/643—Cylindrical 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
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
- H01M10/6561—Gases
- H01M10/6566—Means within the gas flow to guide the flow around one or more cells, e.g. manifolds, baffles or other barriers
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
- H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
- H01M50/213—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for cells having curved cross-section, e.g. round or elliptic
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/284—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders with incorporated circuit boards, e.g. printed circuit boards [PCB]
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/289—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by spacing elements or positioning means within frames, racks or packs
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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
- 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
- H01M50/35—Gas exhaust passages comprising elongated, tortuous or labyrinth-shaped exhaust passages
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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
- 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
- H01M50/35—Gas exhaust passages comprising elongated, tortuous or labyrinth-shaped exhaust passages
- H01M50/358—External gas exhaust passages located on the battery cover or case
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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
- 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
- H01M50/35—Gas exhaust passages comprising elongated, tortuous or labyrinth-shaped exhaust passages
- H01M50/367—Internal gas exhaust passages forming part of the battery cover or case; Double cover vent systems
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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
- 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
- H01M50/383—Flame arresting or ignition-preventing means
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
- H01M50/505—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing comprising a single busbar
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
- H01M50/509—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the type of connection, e.g. mixed connections
- H01M50/512—Connection only in parallel
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
- H01M50/521—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material
- H01M50/522—Inorganic material
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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
- H01M2200/00—Safety devices for primary or secondary batteries
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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 disclosure relates to battery modules in each of which a plurality of batteries are housed in a case, and more particularly to a battery module including a release mechanism for releasing a gas from a battery to outside the case with safety.
- Battery packs in each of which a plurality of batteries are housed in a case so as to output a predetermined voltage and have a predetermined capacity are widely used as power sources for various equipment and vehicles.
- This module technique enables reduction in size and weight of battery modules by enhancing performance of batteries housed in battery modules, and therefore, has advantages such as improved workability in packaging battery packs and high flexibility in installing battery modules in limited space of vehicles or the like.
- Patent Document 1 shows a power source device including a release mechanism in which a case housing a plurality of batteries is divided by a partition into a battery space housing the batteries and a release space through which a high-temperature gas from the batteries is released and in which openings of safety valves of the batteries communicate with an exhaust room.
- This configuration of the release mechanism allows a high-temperature gas from the safety valves of the batteries to flow into the exhaust space while preventing the high-temperature gas from flowing into the battery space, and to be released to outside the case through an outlet of the case. In this manner, it is possible to prevent adjacent batteries from being exposed to a high-temperature gas from an abnormal battery, thereby reducing a harmful influence on normal batteries.
- the release mechanism shown in Patent Document 1 provides a hermetically sealed structure with the exhaust space, thereby preventing a gas which has flown into the release space through an opening of a battery from flowing into the battery space again. For this reason, this release mechanism is advantageous in preventing a secondary degradation of normal batteries.
- a gas which has flown into the exhaust space can be at a high temperature of 1000° C. or more in some cases, and might react with oxygen to cause combustion.
- the exhaust space is exposed to a high temperature, and the batteries housed in the battery space still have the possibility of being affected by the high temperature.
- the present disclosure employs a configuration in which a case housing a plurality of cells is divided by a partition into two spaces: a housing space housing the cells and an exhaust duct for releasing a gas from the cells and in which the exhaust duct is further divided by a partition into two spaces. Openings through which a gas generated in the cells is released communicate with a first space, and the first space communicates with a second space through a through hole formed in the partition.
- a gas from the vents of the cells is adiabatically expanded in the first space to have its temperature reduced to a temperature at which the gas does not cause combustion, and then is adiabatically expanded in the second space to have its temperature reduced to a temperature a temperature at which no significant problems occur even when the gas is released to outside the case. Accordingly, a high-temperature gas from an abnormal battery can be released to outside the case with safety without an influence on other normal batteries. As a result, a safe battery module can be achieved.
- the volume of the first space is adjusted such that when a gas at a high temperature released from the vent of the cell to the first space by adiabatic expansion is released from the first space to the second space, this gas has a temperature equal to or lower than a temperature at which the gas does not cause combustion.
- the volume of the second space is adjusted such that when a gas released from the first space to the second space by adiabatic expansion is released from the second space to outside the case, this gas has a temperature equal to or lower than a temperature at which no significant problems occur even when the gas is released to outside the case.
- a battery module in an aspect of the present disclosure is a battery module in which a plurality of cells are arranged and housed in a case. Each of the cells has a vent through which a gas generated in the cell is released to outside the cell.
- the case is divided, by a flat plate provided at same sides of the cells, into a housing space housing the cells and an exhaust duct for releasing a gas from the vents of the cells to outside the case.
- Each of the vents of the cells communicates with the exhaust duct through an opening formed in the flat plate.
- the exhaust duct is divided into a first space and a second space by a partition provided between the flat plate and an external plate or a bottom of the case. The first space communicates with the second space through a through hole formed in the partition. A gas from the vents of the cells is released to the first space through the opening formed in the flat plate, is guided to the second space through the through hole formed in the partition, and then is released to outside the case.
- the flat plate separating the housing space and the exhaust duct from each other is a circuit board, and the circuit board includes a connection plate on which at least electrodes of the cells at one side are connected in parallel.
- the flat plate separating the housing space and the exhaust duct from each other may be a metal bus bar on which at least electrodes of the cells at one side are connected in parallel.
- the flat plate provided to the same sides of the cells can additionally have a function of electrically connecting the cells, as well as a function of separating the housing space and the exhaust duct from each other. As a result, the size of the battery module can be reduced.
- a high-temperature gas from an abnormal battery can be released to outside a case without an influence on other normal batteries.
- a battery module with a high degree of safety can be obtained.
- FIG. 1 is a cross-sectional view schematically illustrating a configuration of a battery for use in a battery module according to a first embodiment of the present disclosure.
- FIG. 2 is a cross-sectional view schematically illustrating a configuration of the battery module of the first embodiment.
- FIG. 3 is an enlarged cross-sectional view illustrating a portion near an end of a cell to which a flat plate is provided.
- FIG. 4 is a partial cross-sectional view showing a positional relationship between the cell and the flat plate in a case where a vent of the cell is formed in a side of a projection of a positive electrode terminal.
- FIGS. 5( a )- 5 ( c ) are partial cross-sectional views each showing a path of a gas released from vents of cells.
- FIG. 6 is a cross-sectional view schematically illustrating a configuration of a battery module 200 according to a variation of the first embodiment.
- FIGS. 7( a ) and 7 ( b ) are views illustrating a connection structure among electrodes of cells
- FIG. 7( a ) is a disassembled perspective view
- FIG. 7( b ) is an enlarged cross-sectional view illustrating a portion near positive electrode terminals of the cells.
- FIG. 8 is a perspective view illustrating a battery assembly according to a second embodiment of the present disclosure.
- FIG. 9 is a disassembled perspective view illustrating the battery assembly of the second embodiment.
- FIGS. 10( a ) and 10 ( b ) are enlarged views illustrating a region XA and a region XB, respectively, shown in FIG. 9 .
- FIG. 11 shows plan views illustrating a negative electrode bus bar, an insulating plate, and a positive electrode bus bar, respectively, constituting a connection group.
- FIG. 12 is a partial cross-sectional view in which adjacent cells are connected in parallel.
- FIG. 13 is a perspective view illustrating a configuration of a group of battery assemblies in each of which cells are connected in parallel.
- FIG. 14 is a partial cross-sectional view illustrating a connection structure between two cells and taken along the line XIV-XIV in FIG. 13 .
- FIG. 15 is a disassembled perspective view illustrating a battery module according to a specific example of the present disclosure.
- FIG. 16 is a perspective view illustrating the battery module of the specific example.
- FIGS. 17( a ) and 17 ( b ) show a structure of a partition
- FIG. 17( a ) is a perspective view
- FIG. 17( b ) is a plan view.
- FIGS. 18( a ) and 18 ( b ) show a structure of an intermediate panel, FIG. 18( a ) is a perspective view, and FIG. 18( b ) is a plan view.
- FIG. 19 is a cross-sectional view taken along the direction in which the battery assemblies of a battery module are connected in series.
- FIG. 20 is a cross-sectional view schematically illustrating a configuration of a battery module according to a third embodiment.
- FIG. 21 is a plan view illustrating a variation of the battery module of the third embodiment.
- FIG. 22 is a perspective view illustrating a configuration of a battery pack in which a plurality of battery modules are arranged in parallel.
- FIG. 23( a ) is a cross-sectional perspective view illustrating a configuration of a battery module
- FIG. 23( b ) is a partial cross-sectional view of the battery module.
- FIG. 24 is a perspective view in which a first exhaust duct and a second exhaust duct are in contact with one battery module.
- FIG. 25 is a disassembled perspective view illustrating the structure shown in FIG. 24 .
- FIG. 1 is a cross-sectional view schematically illustrating a configuration of a battery 100 to be used in a battery module according to a first embodiment of the present disclosure.
- a battery to be used in the battery module of the present disclosure may be a battery which can be used alone as a power source for mobile electronic equipment such as a laptop computer (and a battery to be used in a battery module will be referred to as a “cell” hereinafter).
- a battery to be used in a battery module will be referred to as a “cell” hereinafter.
- high-performance general-purpose battery can be used as a cell of a battery module, and thus, performance of the battery module can be more easily enhanced at lower cost.
- a cylindrical lithium ion secondary battery as illustrated in FIG. 1 may be employed, for example.
- This lithium ion secondary battery has a general structure, and has a safety mechanism which releases gas to outside the battery when the pressure in the battery increases due to occurrence of, for example, an internal short circuit.
- the structure of the cell 100 will be specifically described with reference to FIG. 1 .
- an electrode group 4 in which a positive electrode 1 and a negative electrode 2 are wound with a separator 3 interposed therebetween is housed in a battery case 7 together with a nonaqueous electrolyte. Insulating plates 9 and 10 are respectively placed on the top and bottom of the electrode group 4 .
- the positive electrode 1 is joined to a filter 12 with a positive electrode lead 5 interposed therebetween.
- the negative electrode 2 is joined to the bottom of the battery case 7 also serving as a negative electrode terminal, with a negative electrode lead 6 interposed therebetween.
- the filter 12 is connected to an inner cap 13 which has a projection joined to a metal safety valve 14 .
- the valve 14 is connected to a terminal plate 8 also serving as a positive electrode terminal.
- the terminal plate 8 , the valve 14 , the inner cap 13 , and the filter 12 serve as a unit, and seal an opening of the battery case 7 with a gasket 11 interposed therebetween.
- the safety mechanism for releasing a gas generated in the cell 100 to the outside is not limited to the structure illustrated in FIG. 1 , and may have other structures.
- FIG. 2 is a cross-sectional view schematically illustrating a structure of a battery module 200 according to this embodiment.
- each of the cells 100 includes the vent 8 a for releasing a gas generated in the cell 100 to outside the cell 100 .
- the case 20 is divided into a housing space 50 housing a plurality of cells 100 and an exhaust duct 60 for releasing a gas from the vents 8 a of the cells 100 to outside the case 20 , by a flat plate 30 disposed at the same sides (toward the positive electrode terminals 8 in this embodiment) of the cells 100 .
- the vents 8 a of the cells 100 communicate with the exhaust duct 60 through openings 30 a formed in the flat plate 30 .
- the exhaust duct 60 is divided, by a partition 40 placed between the flat plate 30 and an external plate (lid) 21 of the case 20 , into a first space 61 defined between the partition 40 and the flat plate 30 and a second space 62 defined between the partition 40 and the external plate 21 of the case 20 .
- the first space 61 communicates with the second space 62 through a through hole 40 a formed in the partition 40 .
- the exhaust duct thus configured allows a gas from the vents 8 a of the cells 100 to be released to the first space 61 through the openings 30 a formed in the flat plate 30 , guided to the second space 62 through the through holes 40 a in the partition 40 , and then released to outside the case 20 through a release outlet 22 provided in the case 20 .
- the flat plate 30 is in close contact with the same sides (i.e., toward the positive electrode terminals 8 in this embodiment) of the cells 100 , and thus, the housing space 50 is hermetically sealed by the flat plate 30 . Accordingly, a gas released to the first space 61 from the vents 8 a of the cells 100 through the openings 30 a of the flat plate 30 does not return to the housing space 50 again.
- FIG. 3 is an enlarged cross-sectional view illustrating a portion near an end of a cell 100 to which the flat plate 30 is provided.
- a shoulder 7 a of the battery case 7 and the flat plate 30 are in close contact with each other with the elastic member 31 interposed therebetween. Accordingly, a gas released from the vent 8 a formed in the projection of the positive electrode terminal 8 does not return to the housing space again because the housing space of the cell 100 is hermetically sealed by the flat plate 30 .
- the elastic member 31 may be adhesive. In this case, the cell 100 can be held by the flat plate 30 .
- the flat plate 30 may be in direct contact with the shoulder 7 a of the battery case 7 with the elastic member 31 not interposed therebetween.
- FIG. 4 is a partial cross-sectional view showing a positional relationship between the cell 100 and the flat plate 30 in a case where a vent 8 a of the cell 100 is formed in a side of the projection of the positive electrode terminal 8 .
- the opening 30 a formed in the flat plate 30 has a ring shape, and thus, the battery case 7 and the flat plate 30 can be in close contact with each other even on a flat portion of the projection of the positive electrode terminal 8 .
- This configuration allows the elastic member to be adhesive, thereby further enhancing the function of holding the cell 100 .
- the “flat plate 30 ” herein is not necessarily flat, and may be a plate having unevenness according to the shape of the battery case 7 , for example, as long as the plate is flat as a whole.
- the state of being “hermetically sealed” herein does not necessarily mean a state of being completely sealed, and includes a sealed state in which a negligible amount of gas returns from the exhaust duct 60 to the housing space 50 .
- a gas released from the vents 8 a of the cells 100 to the exhaust duct 60 is adiabatically expanded in the exhaust duct 60 , thereby causing a decrease in temperature of the gas.
- the gas released from the vents 8 a of the cells 100 can be at a temperature of 1000° C. or more in some cases, if the temperature of the adiabatically expanded gas does not decrease to a temperature at which the gas does not react with oxygen, the gas might react with ambient oxygen to cause combustion.
- the gas temperature decrease due to adiabatic expansion depends on the capacity of the exhaust duct. Since the gas released to the exhaust duct is released to outside the case 20 while pushing oxygen in the exhaust duct out, the amount of a gas which reacts with oxygen to cause combustion during adiabatic expansion depends on the volume of the exhaust duct (i.e., the amount of oxygen). Accordingly, to prevent a gas released from the vents 8 a of the cells 100 from reacting with oxygen to continuously cause combustion, it is necessary to cause adiabatic expansion in an exhaust duct whose volume is as small as possible so as to reduce the gas temperature to a temperature at which the gas does not react with oxygen. To satisfy this necessity, the volume of the exhaust duct needs to be controlled near the vents 8 a of the cells 100 through which a high-temperature gas is released.
- the first space 61 of the present disclosure is provided to achieve the control described above.
- the volume of the first space 61 is adjusted such that when a gas at a high temperature released from the vent 8 a of the cell 100 to the first space 61 by adiabatic expansion is released from the first space 61 to the second space 62 , this gas has a temperature equal to or lower than a temperature at which the gas does not react with oxygen.
- the volume of the first space 61 can be appropriately adjusted in consideration of performance of the cells 100 to be used, the type of an electrolyte (i.e., the type of a gas to be generated).
- the volume of the first space 61 for achieving the temperature described above may be obtained through a simulation using a model of adiabatic expansion, or may be obtained through various experiments. Specifically, as an example of a simple experiment, the vent 8 a of the cell 100 is formed to have a space having a certain volume, and a release outlet from this space to the atmosphere is provided. Then, a nail is driven in the battery case 7 of the cell 100 to cause an internal short circuit as a simulation, resulting in gushing of a high-temperature gas from the vent 8 a . By selecting the volume of the space, the gas otherwise gushing from the release outlet with a spark and fire can be changed into smoke in a state in which fire has been extinguished. In this manner, the volume of the first space 61 can be determined.
- the first space 61 communicates with the second space 62 through the through holes 40 a formed in the partition 40 . Accordingly, the location of the through holes 40 a affects a path through which a high-temperature gas from the vents 8 a of the cells 100 flows from the first space 61 to the second space 62 . In view of this, the volume of the first space 61 may be further adjusted in consideration of the location of the through holes 40 a.
- the space 61 is not open but closed in the lateral direction in FIG. 5( a ). Accordingly, as illustrated in FIG. 5( a ), in a case where the through holes 40 a are arranged at the same pitch as the cells 100 , a path through which a high-temperature gas from the vents 8 a of the cells 100 flows from the first space 61 to the second space 62 is a path indicated by arrows in most part.
- the first space 61 is expected to be substantially controlled by a space in the range indicated by A.
- a path through which a high-temperature gas from the vents 8 a of the cells 100 flows from the first space 61 to the second space 62 is a path indicated by arrows in most part.
- the first space 61 is expected to be substantially controlled by a space in the range indicated by B.
- the location of the through holes 40 a can substantially control the volume of the first space 61 .
- the volume of the first space 61 may be controlled by further dividing the first space into a plurality of subspaces 63 by side walls 41 .
- the control of the first space 61 is not strictly defined. Effective advantages of the present disclosure can be achieved by dividing the exhaust duct 60 into the first space 61 and the second space 62 to adjust the volume of the first space 61 communicating with the vents 8 a of the cells 100 .
- the volume of the second space 62 is adjusted such that when a gas released from the first space 61 to the second space 62 by adiabatic expansion is released from the second space 62 to outside the case 20 , the gas has a temperature equal to or lower than a temperature at which no significant problems occur even when the gas is released to outside the case. Since the gas released from the space 61 to the second space 62 is changed to be at a temperature at which the gas does not react with oxygen in the first space 61 , the possibility of combustion of the gas is eliminated in the second space 62 .
- each of the external plate 21 and the partition 40 may be made of a material having a high thermal conductivity, such as aluminium or iron. In this case, an advantage of a temperature decrease by conduction of heat can be achieved in addition to an advantage of a temperature decrease by adiabatic expansion.
- the exhaust duct 60 is divided into the first space 61 and the second space 62 .
- the exhaust duct 60 may be divided into three or more spaces by a plurality of partitions.
- the second space 62 is not necessarily formed between the partition 40 and the case 20 .
- the second space 62 may be placed between the partition 40 and a second partition provided between the partition 40 and the external plate 21 .
- the space formed between the second partition and the external plate may be a flow path through which a refrigerant flows. This configuration can more efficiently reduce the temperature of a gas in the second space 62 .
- the vents 8 a of the cells 100 are formed in projections (flat portions or sides) of the positive electrode terminals 8 , but may be formed in the bottoms of the battery case 7 serving as the negative electrode terminals.
- the flat plate 30 is provided toward the negative electrode terminals of the cells 100
- the exhaust duct 60 is formed between the flat plate 30 and the bottom of the case 20 .
- the vents 8 a formed in the bottoms of the battery cases 7 communicate with the exhaust duct 60 through the openings 30 a formed in the flat plate 30 .
- the exhaust duct 60 is separated from the housing space 50 by a plate disposed at the same sides (i.e., toward the positive electrode terminals or the negative electrode terminals) of the cells 100 .
- This configuration is obtained by arranging the cells 100 in the case 20 with the polarities of the cells 100 oriented in the same direction.
- FIG. 6 is a cross-sectional view schematically illustrating a configuration of the battery module 200 according to a variation of the first embodiment. As illustrated in FIG. 6 , this variation is different from the first embodiment in that the cells 100 are arranged with their polarities alternately oriented in opposite directions.
- the cells 100 are housed in the case 20 in such a manner that the positions of the positive electrode terminals 8 alternate between the top and the bottom, specifically, the positive electrode terminal 8 of the cell 100 a is positioned at the top and the positive electrode terminal 8 of the cell 100 b adjacent to the cell 100 a is positioned at the bottom.
- the vents 8 a from which a gas generated in the cells 100 is released are formed in the projections of the positive electrode terminals 8 .
- the flat plate 30 separating the housing space 50 and the exhaust duct 60 is disposed at each end of each of the cells 100 , resulting in that the exhaust duct 60 is formed as two exhaust ducts 60 a and 60 b respectively located at the bottom and the top of the case 20 and sandwiching the housing space 50 .
- Each of the vents 8 a of the cells 100 communicates with one of the exhaust ducts 60 a and 60 b through the opening 30 a formed in the flat plate 30 .
- the exhaust duct 60 a at the top of the case 20 is divided, by a partition 40 placed between the flat plate 30 and the external plate 21 of the case 20 , into a first space 61 a formed between the partition 40 and the flat plate 30 and a second space 62 a formed between the partition 40 and the external plate 21 of the case 20 .
- the first space 61 a communicates with the second space 62 a through the through holes 40 a formed in the partition 40 .
- the exhaust duct 60 b at the bottom of the case 20 is divided, by a partition 40 placed between the flat plate 30 and the bottom 23 of the case 20 , into a first space 61 b formed between the partition 40 and the flat plate 30 and a second space 62 b formed between the partition 40 and the bottom 23 of the case 20 .
- the first space 61 b communicates with the second space 62 b through the through holes 40 a formed in the partition 40 .
- a gas is released from the vents 8 a of the cells 100 to the first space 61 a , 61 b through the openings 30 a formed in the flat plate 30 , is guided to the second space 62 a , 62 b through the through holes 40 a formed in the partition 40 , and then is released to outside the case 20 through the release outlet 22 provided in the case 20 .
- connection plate can be advantageously formed to be in the shape of a simple plate in connecting the cells 100 in series.
- the housing space 50 housing the cells 100 and the exhaust duct 60 for releasing a gas from the vents 8 a of the cells 100 are separated from each other by the flat plate 30 .
- the flat plate 30 may have a function of electrically connecting the electrodes of the cells 100 .
- FIGS. 7( a ) and 7 ( b ) are views illustrating a connection structure among the electrodes of the cells 100 connected in a line (hereinafter referred to as a “battery assembly”). Specifically, FIG. 7( a ) is a disassembled perspective view, and FIG. 7( b ) is an enlarged cross-sectional view illustrating a portion near positive electrode terminals 8 of the cells 100 .
- a positive electrode connection plate 70 and a negative electrode connection plate 73 are formed on the surface of a circuit board 30 , and openings 70 a are formed in the positive electrode connection plate 70 .
- openings 30 a are formed in the circuit board 30 .
- Negative electrode terminals of the cells 100 i.e., the bottoms of the battery cases
- are connected in parallel by a negative electrode bus bar 81 and are connected to the negative electrode connection plate 73 on the circuit board 30 through a conductive part 72 extending from the negative electrode bus bar 81 .
- the cells 100 are connected in parallel by the positive electrode connection plate 70 and the negative electrode connection plate 73 formed on the circuit board 30 .
- projections of positive electrode terminals 8 of the cells 100 are inserted in the openings 30 a of the circuit board 30 to be connected to the positive electrode connection plate 70 formed on the circuit board 30 .
- the circuit board 30 is brought into contact with the battery cases with an elastic member 31 interposed therebetween.
- the vents 8 a of the cells 100 communicate with an exhaust duct (not shown) through the openings 70 a of the positive electrode connection plate 70 .
- a gas from the vents 8 a of the cells 100 is released to the exhaust duct through openings 30 a formed in the circuit board 30 .
- the circuit board 30 hermetically seals a housing space (not shown) for the cells 100 , the gas released to the exhaust duct does not return to the housing space again.
- the flat plate 30 having the function of electrically connecting the electrodes of the cells 100 is not necessarily a circuit board made of an insulating member, and may be a connection plate made of a metal member (hereinafter referred to as a “metal bus bar”).
- connection structure among the electrodes of the cells 100 using a metal bus bar will be described hereinafter with reference to FIGS. 8-14 .
- FIG. 8 is a perspective view illustrating a battery assembly 300 according to this embodiment.
- FIG. 9 is a disassembled perspective view illustrating the battery assembly 300 .
- the battery cases of the cells 100 are exposed in this embodiment. Accordingly, in the cells 100 , not only the bottom surfaces of the battery cases but also side surfaces and top surfaces thereof can serve as negative electrode terminals.
- the positive electrode bus bar 83 and the negative electrode bus bar 81 connecting the positive electrodes and the negative electrodes of the cells 100 in parallel are in contact with the battery cases with the insulating plate 82 interposed between of the battery case and the bus bars 83 and 81 at the side of the positive electrode terminals of the cells 100 .
- the positive electrode terminals 8 of the cells 100 are connected to the positive electrode bus bar 83 through positive electrode connection strips 84 .
- connection group 85 including the negative electrode bus bar 81 , the insulating plate 82 , the positive electrode bus bar 83 , and the connection strips 84 is locally placed at the side of the positive electrode terminals 8 of the cells 100 , thereby further reducing the size of the battery assembly 300 .
- the negative electrode bus bar 81 and the positive electrode bus bar 83 have specific shapes, which will be described later.
- FIGS. 10( a ) and 10 ( b ) are enlarged views illustrating a region XA and a region XB, respectively, shown in FIG. 9 .
- FIG. 11 shows plan views illustrating the negative electrode bus bar 81 , the insulating plate 82 , and the positive electrode bus bar 83 , respectively, constituting the connection group 85 .
- FIG. 12 is a partial cross-sectional view in which adjacent cells 100 are connected in parallel.
- the negative electrode bus bar 81 is, for example, a nickel plate having a thickness of 0.2 mm, and is configured to be in contact with the battery cases (i.e., the negative electrode terminals) of the cells 100 constituting the battery assembly 300 . As illustrated in FIG. 10( a ), this negative electrode bus bar 81 has a stepped portion 81 b extending along the longitudinal direction, and through holes 81 a and negative electrode connection strips 81 c are arranged to be spaced from one another along the longitudinal direction. As illustrated in FIG. 12 , when the negative electrode bus bar 81 is brought into contact with the battery cases, the positive electrode terminals 8 of the cells 100 are exposed in the through holes 81 a .
- the negative electrode connection strips 81 c are welded to the outer peripheries of the battery cases to be fixed to the battery cases.
- the bottoms (i.e., the negative electrode terminals) of the battery cases of the cells 100 may be connected in parallel by another metal bus bar 88 . In this case, the cells 100 can also be fixed.
- the positive electrode bus bar 83 is, for example, a copper plate having a thickness of about 1 mm, and is provided on the negative electrode bus bar 81 with the insulating plate 82 interposed therebetween. As illustrated in FIG. 11 , the positive electrode bus bar 83 and the insulating plate 82 respectively have through holes 83 a and 82 a .
- the through holes 83 a are spaced from one another along the longitudinal direction, and the through holes 82 a are also spaced from one another along the longitudinal direction.
- the through holes 81 a , 82 a , and 83 a of the negative electrode bus bar 81 , the insulating plate 82 , and the positive electrode bus bar 83 communicate with one another. In this manner, as illustrated in FIG. 12 , the positive electrode terminals 8 of the cells 100 are exposed in the through holes 81 a , 82 a , and 83 a.
- Each of the positive electrode connection strips 84 is, for example, a nickel plate having a thickness of 0.2 mm, and as illustrated in FIG. 10( b ), has a first connection strip 84 a , a second connection strip 84 b , and a stepped portion 84 c .
- the first connection strip 84 a and the second connection strip 84 b sandwich the stepped portion 84 c , and have different heights.
- the first connection strips 84 a are connected to the positive electrode terminals 8 of the cells 100
- the second connection strips 84 b are connected to the upper surface of the positive electrode bus bar 83 . In this manner, the positive electrode terminals 8 of the cells 100 are connected to the positive electrode bus bar 83 through the positive electrode connection strips 84 .
- connection structure among the electrodes in a case where a plurality of battery assemblies 300 illustrated in FIG. 8 are arranged to form a group of the battery assemblies will be described.
- FIG. 13 is a perspective view illustrating a configuration of a group of four battery assemblies 300 in each of which 10 cells 100 are connected in parallel.
- FIG. 14 is a partial cross-sectional view illustrating a connection structure between two cells 100 and taken along the line XIV-XIV in FIG. 13 .
- the negative electrode bus bar 81 and the positive electrode bus bar 83 are in contact with the battery cases 7 of the cells 100 with the insulating plate 82 interposed therebetween.
- an end 83 b of the positive electrode bus bar 83 in the lateral direction and the stepped portion 81 b of the negative electrode bus bar 81 in the lateral direction project in opposite directions with respect to a center line L connecting the centers of the through holes 83 a , 82 a , and 81 a . Accordingly, in adjacent cells 100 A and 100 B illustrated in FIG.
- FIG. 15 is a disassembled perspective view illustrating a battery module of this specific example.
- FIG. 16 is a perspective view illustrating the battery module.
- a temperature adjustment unit 90 As illustrated in FIG. 15 , a temperature adjustment unit 90 , a battery assembly group 400 , a resin intermediate panel 93 , and a metal (e.g., aluminium) partition 40 are housed in a resin case 20 .
- the top of the case 20 is covered with a metal (e.g., aluminium) external plate (lid) 21 .
- the front of the case 20 is covered with a resin front panel 94 .
- the battery assembly group 400 seven battery assemblies 300 each including 20 parallel-connected cells 100 are connected in series.
- the cells 100 are series-parallel connected, i.e., connected in series in some places and in parallel in other places, by the connection group 85 illustrated in FIG. 9 .
- a positive electrode terminal 87 of the battery assembly group 400 is connected to one of the positive electrode bus bars 83 constituting the battery assemblies 300 (see FIG. 12 ), and are connected to a positive electrode terminal 96 for external connection provided on the front panel 94 .
- a negative electrode terminal 86 of the battery assembly group 400 is connected to one of the negative electrode bus bars constituting the battery assemblies 300 (see FIG. 12 ), and are connected to a negative electrode terminal 95 for external connection provided on the front panel 94 .
- FIGS. 17( a ) and 17 ( b ) show a structure of the partition 40 .
- FIG. 17( a ) is a perspective view
- FIG. 17( b ) is a plan view.
- the partition 40 is made of, for example, aluminium.
- a plurality of through holes 40 a are formed at positions corresponding to the positive electrode terminals 8 of the cells 100 .
- projections 40 b are arranged in two lines.
- FIGS. 18( a ) and 18 ( b ) show a structure of the intermediate panel 93 .
- FIG. 18( a ) is a perspective view
- FIG. 18( b ) is a plan view.
- the intermediate panel 93 is made of, for example, a resin, and is partitioned into four hollow portions 93 a along the parallel connection of the battery assemblies 300 , as illustrated in FIGS. 18 ( a ) and 18 ( b ).
- the temperature adjustment unit 90 has holding portions 90 a in which the cells 100 constituting the battery assembly group 400 are inserted to be held.
- a flow path though which a fluid flows is formed among the holding portions 90 a , 90 a , . . . .
- inlet and outlet tubes 91 and 92 for supplying a fluid to the flow path are connected to the front panel 94 of the temperature adjustment unit 90 , and are inserted in through holes 98 and 99 formed in the front panel 94 .
- FIG. 19 is a cross-sectional view taken along the direction in which the battery assemblies 300 of battery modules are connected in series.
- the cells 100 are housed in the holding portions 90 a of the temperature adjustment unit 90 , and have their temperatures adjusted by the fluid flowing in a flow path 97 .
- the case 20 is partitioned, by the connection group 85 provided on the positive electrode terminals 8 of the cells 100 , into a housing space housing the cells 100 and an exhaust duct 60 for releasing a gas from the vents 8 a of the cells 100 to outside the case 20 .
- the vents 8 a of the cells 100 communicate with the exhaust duct 60 through the through holes 83 a , 82 a , and 81 a of the negative electrode bus bar 81 , the insulating plate 82 , and the positive electrode bus bar 83 constituting the connection group 85 .
- the exhaust duct 60 is divided into a first space 61 and a second space 62 by a partition 40 provided between the connection group 85 and the external plate 21 of the case 20 .
- the first space 61 communicates with the second space 62 through the through holes 40 a formed in the partition 40 .
- the first space 61 is divided into a plurality of subspaces by hollow portions 93 a formed in the intermediate panel 93 .
- a gas from the vents 8 a of the cells 100 is released to the first space 61 (i.e., the subspaces) through the through holes 83 a , 82 a , and 81 a of the connection group 85 , and is guided to the second space 62 through the through holes 40 a formed in the partition 40 , and then is released to outside the case 20 through the release outlet 22 formed in the front panel 94 .
- the exhaust duct 60 is divided into the first space 61 and the second space 62 by the partition 40 , a gas released from the first space 61 to the second space 62 has a temperature equal to or lower than a temperature at which the gas does not react with oxygen, and thus, the possibility of combustion of a gas is eliminated in the second space 62 .
- the second space 62 does not need to have a volume as small as possible for adiabatic expansion, and is allowed to have a relatively large volume as compared to the first space.
- an exhaust space corresponding to the second space 62 does not need to be provided in the case 20 housing a plurality of cells 100 .
- a battery module according to this embodiment employs a configuration in which a first exhaust space (corresponding to the first space 61 ) defined by a flat plate 30 placed at the same sides of the cells 100 is provided in a case 20 and a second exhaust space (corresponding to the second space 62 ) communicating with the first exhaust space is provided to be in contact with the case 20 .
- the volume of the first exhaust space is adjusted such that when a gas released from vent 8 a of the cell 100 to the first exhaust space by adiabatic expansion is released from the first exhaust space to the second exhaust space, this gas has a temperature equal to or lower than a temperature at which the gas does not react with oxygen.
- FIG. 20 is a cross-sectional view schematically illustrating a configuration of a battery module 200 according to this embodiment.
- a plurality of cells 100 are arranged and housed in a case 20 .
- the cells 100 have vents 8 a through which a gas generated in the cells 100 is released to outside the cells 100 .
- the case 20 is divided, by a flat plate 30 provided at the same sides of the cells 100 , into a housing space 50 housing the cells 100 and a first exhaust space 61 c from which a gas from the vents 8 a of the cells 100 is released to outside the case 20 through a release outlet 22 provided in the case 20 .
- the vents 8 a of the cells 100 communicate with the first exhaust space 61 c through openings 30 a formed in the flat plate 30 .
- an exhaust duct 65 including a second exhaust space 62 c having an aperture 66 a communicating with the release outlet 22 is in contact with the case 20 .
- a gas from the vents 8 a of the cells 100 is released to the first exhaust space 61 c through the openings 30 a formed in the flat plate 30 , is guided to the second exhaust space 62 c through the aperture 66 a , and then is released to outside the case 20 through a release outlet 66 b formed in the exhaust duct 65 .
- the case 20 and the exhaust duct 65 may be formed as an integrated unit.
- the battery module 200 includes the housing space 50 , the first exhaust space 61 c , and the exhaust duct 65 .
- FIG. 21 is a plan view illustrating a variation of the battery module shown in FIG. 20 .
- a plurality of (four in FIG. 21 ) of battery modules 200 in each of which a plurality of cells 100 are aligned are arranged in parallel.
- an exhaust duct 65 including apertures 66 a communicating with the respective release outlets 22 of the battery modules 200 may be provided to be in contact with the cases 20 of the battery modules 200 .
- the exhaust duct 65 shared by the battery modules 200 can increase the substantial volume ratio of the exhaust duct 65 to the exhaust spaces 61 c of the battery modules 200 .
- a temperature decrease due to adiabatic expansion of a gas released from the first exhaust space 61 c to the second exhaust space 62 c can be facilitated.
- FIG. 22 is a perspective view illustrating a configuration of a battery pack in which a plurality of (four in FIG. 22 ) battery modules 200 including series-parallel connected cells 100 housed in the case 20 as shown in FIG. 15 are arranged in parallel.
- the battery modules 200 are in contact with the exhaust ducts 65 including the second exhaust spaces 62 c .
- the first exhaust ducts 65 are in contact with second exhaust ducts 67 including third exhaust spaces 67 c.
- FIG. 23( a ) is a cross-sectional perspective view illustrating a configuration of the battery module 200 .
- FIG. 23( b ) is a partial cross-sectional view of the battery module 200 .
- FIG. 24 is a perspective view in which the first exhaust duct 65 and the second exhaust duct 67 are in contact with one battery module 200 .
- FIG. 25 is a disassembled perspective view illustrating the structure shown in FIG. 24 .
- the first exhaust duct 65 has a plurality of apertures 66 a communicating with the first exhaust space 61 c of the battery module 200
- the second exhaust duct 67 has a plurality of apertures 68 a communicating with the release outlet 66 b of each of the first exhaust ducts 65 .
- a gas from the vents 8 a of the cells 100 is released to the first exhaust space 61 c , is guided to the second exhaust space 62 c through the apertures 66 a , and then is released to the outside through a release outlet 68 b provided in the second exhaust duct 67 .
- the cells 100 are lithium ion secondary batteries, but may be other secondary batteries (e.g., nickel-metal hydride batteries).
- the present disclosure is useful for power sources for driving automobiles, electric motorcycles, and electric play equipment, for example.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Mounting, Suspending (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Connection Of Batteries Or Terminals (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2009216463A JP5466906B2 (ja) | 2009-09-18 | 2009-09-18 | 電池モジュール |
JP2009-216463 | 2009-09-18 | ||
PCT/JP2010/004674 WO2011033713A1 (ja) | 2009-09-18 | 2010-07-21 | 電池モジュール |
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PCT/JP2010/004674 A-371-Of-International WO2011033713A1 (ja) | 2009-09-18 | 2010-07-21 | 電池モジュール |
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US14/144,305 Continuation US8956747B2 (en) | 2009-09-18 | 2013-12-30 | Battery module |
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US20120164490A1 true US20120164490A1 (en) | 2012-06-28 |
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US14/595,842 Abandoned US20150140369A1 (en) | 2009-09-18 | 2015-01-13 | Battery module |
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US14/144,305 Active US8956747B2 (en) | 2009-09-18 | 2013-12-30 | Battery module |
US14/595,842 Abandoned US20150140369A1 (en) | 2009-09-18 | 2015-01-13 | Battery module |
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US (3) | US20120164490A1 (ja) |
EP (1) | EP2475028B1 (ja) |
JP (1) | JP5466906B2 (ja) |
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CN (1) | CN102473884B (ja) |
WO (1) | WO2011033713A1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
US20150140369A1 (en) | 2015-05-21 |
EP2475028B1 (en) | 2014-04-30 |
EP2475028A1 (en) | 2012-07-11 |
WO2011033713A1 (ja) | 2011-03-24 |
EP2475028A4 (en) | 2012-11-21 |
JP2011065906A (ja) | 2011-03-31 |
CN102473884A (zh) | 2012-05-23 |
KR20120090027A (ko) | 2012-08-16 |
US20140113167A1 (en) | 2014-04-24 |
KR101269721B1 (ko) | 2013-05-30 |
CN102473884B (zh) | 2014-08-27 |
US8956747B2 (en) | 2015-02-17 |
JP5466906B2 (ja) | 2014-04-09 |
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