EP2384519A1 - Modulare cid-anordnung für lithium-ionen-akkumulator - Google Patents
Modulare cid-anordnung für lithium-ionen-akkumulatorInfo
- Publication number
- EP2384519A1 EP2384519A1 EP10702959A EP10702959A EP2384519A1 EP 2384519 A1 EP2384519 A1 EP 2384519A1 EP 10702959 A EP10702959 A EP 10702959A EP 10702959 A EP10702959 A EP 10702959A EP 2384519 A1 EP2384519 A1 EP 2384519A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- battery
- disc
- current interrupt
- interrupt device
- pressure disc
- 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.)
- Withdrawn
Links
- 229910001416 lithium ion Inorganic materials 0.000 title description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 7
- 238000007789 sealing Methods 0.000 claims abstract 5
- 238000003466 welding Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- 238000004891 communication Methods 0.000 claims description 33
- 229910052782 aluminium Inorganic materials 0.000 claims description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000013022 venting Methods 0.000 claims description 4
- 230000035515 penetration Effects 0.000 claims description 3
- 230000000284 resting effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- 230000004913 activation Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000037361 pathway Effects 0.000 description 6
- -1 Li+ Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 206010010099 Combined immunodeficiency Diseases 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000001360 collision-induced dissociation Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002788 crimping Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M50/528—Fixed electrical connections, i.e. not intended for disconnection
-
- 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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
-
- 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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/578—Devices or arrangements for the interruption of current in response to pressure
-
- 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
- H01M50/342—Non-re-sealable arrangements
- H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- Li-ion batteries in portable electronic devices typically undergo different charging, discharging and storage routines based on their use. Batteries that employ Li-ion cell chemistry will produce gas when they are electrically overcharged beyond established safety limits. This gas may be used to trigger pressure activated safety devices to improve the reliability and safety of batteries.
- a current interrupt device is typically employed to provide protection against any excessive internal pressure increase in a battery by interrupting the current path from the battery when pressure inside the battery is greater than a predetermined value.
- the CID typically includes a rupture disc and a pressure disc in electrical communication with each other. The rupture disc and the pressure disc are, in turn, in electrical communication with an electrode and a terminal of the battery, respectively.
- the pressure disc separates from (e.g., deforms away or is detached from) the rupture disc of the CID when pressure inside the battery is greater than a predetermined value, whereby a current flow between the electrode and the terminal is interrupted.
- CIDs known in the art activate at a relatively high pressure, for example, at an internal gauge pressure greater than about 15 kg/cm 2 .
- the internal temperature of the battery is also relatively high, causing additional safety issues. High temperatures are a particular concern in relatively large cells, such as cells larger than " 18650" cells (which have an outer diameter of about 18 mm and a length of 65 mm).
- CIDs typically are fabricated in conjunction with fabrication of the remainder of the battery and require a low tolerance for variation to ensure activation at an appropriate pressure
- the surface area available for welding of a tab from the jelly roll of a battery typically is limited due to need to provide gas pressure conduits.
- the gas pressure conduits in the disc often includes at least one through-hole that must not be blocked during welding of tabs from the jellyroll to the rupture disc.
- the surface area of the pressure disc is one of the factors that affect its actuation or reversal pressure, material thickness being another.
- the shortest side of the cell typically dictates the maximum size of a circular pressure disc that can be used.
- it is possible to achieve lower activation or reversal pressures by using an elongated pressure disc (oblong, oval, etc.) compared to a circular pressure disc of the same material thickness.
- the present invention generally is directed to a modular current interrupt device, a battery that includes a modular current interrupt device of the invention, and a method of forming a modular current interrupt device of the invention.
- the modular current interrupt device includes an electrically-conductive rupture disc and an electrically-conductive pressure disc attached to the rupture disc to form an electrical pathway.
- An electrically-insulating ring partitions a perimeter of the rupture disc from a perimeter of the pressure disc.
- a seating element of the current interrupt device secures the electrically-insulating ring to the pressure disc, At least one of the ruptured discs and the electrically- insulating ring defines a conduit, whereby exposure of one side of the pressure disc to sufficient pressure through the conduit will cause the pressure disc to separate from the rupture disc to thereby sever the electrical pathway.
- the seating element can be electrically conductive and electrically connected to the pressure disc.
- the rupture disc and the electrically-insulating ring together can define the conduit.
- the rupture disc can include a plurality of retention points that form an interference fit with the electrically-insulating ring.
- the perimeter of the rupture disc can be a polygon.
- the polygon can define the retention points.
- the polygon can have from 10 sides to 20 sides, such as 14 sides.
- the conduit can be defined in part by the perimeter of the rupture disc.
- the perimeter of the rupture disc can be beveled.
- the perimeter of the rupture disc can include a double bevel.
- the angle of at least one of the bevels can be in a range of between about 40 degrees and about 55 degrees, such as about 47 degrees. In some embodiments, the angle of both bevels can be about 47 degrees.
- the electrically insulating ring can define a lip at a periphery of the ring, whereby the lip overlaps the periphery of the rupture disc.
- the rupture disc can define a groove at the periphery of the rupture disc, whereby the lip of the insulating ring overlaps the rupture disc at the groove, and a surface of the lip of the insulating ring can be essentially flush with a surface of the rupture disc.
- the electrically insulating ring can define at least one channel that, together with the rupture disc, defines at least a portion of the conduit. The channel can have a major axis that is essentially normal to a tangent of a circle defined by the electrically- insulating ring.
- the rupture disc, the pressure disc and the seating element can be aluminum.
- the electrically- insulating ring can include a polymer.
- the rupture disc can define at least one conduit.
- the electrically-insulating ring defines at least one conduit at a periphery of the ring, whereby fluid communication exists between a frustoconical component of the pressure disc and an external surface of the current interrupt device.
- the pressure disc can further include an elevated surface and a peripheral base, the elevated surface being linked to the peripheral base by the frustoconical component, and wherein the rupture disc is electrically connected to the pressure disc at the elevated surface.
- the pressure disc can be electrically connected to the rupture disc at at least one point. The point can include a weld.
- the seating element can be electrically-conductive.
- the pressure disc can be in electrical communication with the seating element, and the seating element can secure the electrically-insulating ring to the pressure disc by a crimp at a periphery of the seating device.
- the seating element can define a seating element conduit.
- the rupture disc can define the conduit,
- the invention is a battery, such as a lithium-ion based battery, that includes a modular current interrupt device, wherein the current interrupt device includes an electrically-conductive rupture disc and an electrically- conductive pressure disc attached to the rupture disc to form an electrical pathway.
- the battery also includes a first terminal in electrical communication with a first electrode of the battery, a second terminal in electrical communication with a second electrode of the battery, and a battery can having a cell casing and a lid which are in electrical communication with each other, the battery can being electrically insulated from the first terminal, wherein at least a portion of the battery can is at least a component of the second terminal, or is electrically connected to the second terminal.
- the cell casing can be a prismatic cell casing.
- An electrically-insulating ring partitions a perimeter of the rupture disc from the perimeter of the pressure disc.
- a seating element of the current interrupt device secures the electrically-insulating ring to the pressure disc.
- At least one of the rupture disc and the electrically- insulating ring define a conduit, whereby exposure of one side of the pressure disc to sufficient pressure through the conduit will cause the pressure disc to separate from the rupture disc to thereby sever an electrical pathway.
- the modular current interrupt device is at a recessed portion of a lid of the battery, the recessed portion defining an opening in the lid.
- the modular current interrupt device can be a component of a positive terminal of the battery.
- At least one lead of a positive terminal of the battery can be in electrical communication with the rupture disc of the modular current interrupt device.
- the current interrupt device can be in electrical communication with the battery can.
- the current interrupt device can be in electrical communication with the lid of the battery can, and the lid can include a recess facing toward the pressure disc. The recess can be co-terminous with the perimeter of the first end of a frustum variant.
- a method of forming a modular current interrupt device includes combining a pressure disc and a seating element of the current interrupt device, and combining a rupture disc and an electrically-insulating ring, The combined pressure disc and seating element and the combined rupture disc and electrically-insulating ring are then assembled, and the rupture disc is laser or resistance spot welded to the pressure disc to form an electrical pathway therebetween.
- the method can include welding the rupture disc on at least one spot, preferably on two spots, onto an essentially planar cap of the pressure disc while a temperature of the pressure disc is controlled so as not to melt through the pressure disc opposite the weld.
- a battery can be formed by subsequently placing the modular current interrupt device within a recessed portion of a lid of the battery, wherein the recessed portion defines an opening of the lid, attaching either a first electrode or a second electrode of the battery to the current interrupt device, attaching the current interrupt device onto a battery can of the battery, the battery can including a cell casing and a lid which are in electrical communication with each other, and forming a first terminal in electrical communication with the first electrode, and a second terminal in electrical communication with the second electrode.
- the method can further include welding the current interrupt device onto the lid of the battery can.
- Welding of the current interrupt device onto the lid of the battery can be performed by seam welding a circumferential interface between the lid and the pressure disc of the current interrupt device, preferably by penetration welding at the base of the pressure disc.
- the method can further include the step of welding the lid of the battery can onto the cell casing of the battery can.
- the electrical communication can be interrupted when a gauge pressure between the discs is in a range of, for example, between about 4 kg/cm and about 10 kg/cm or between about 4 kg/cm and about 9 kg/cm .
- the weld connecting the lid and the cell casing ruptures when a gauge pressure between the lid and the cell casing is greater than or equal to about 20 kg/cm 2 .
- the method can further include the step of the step of forming at least one venting means on the cell casing, wherein gaseous species inside the battery exit through the venting means when an internal gauge pressure is in a range of between about 10 kg/cm 2 and about 20 kg/cm 2 .
- the present invention is directed to a CID comprising a pressure disc that includes a frustum variant having a first end and a second end, wherein a cross-section of at least one of the first or second ends is non- circular.
- a base extends radially from a perimeter of the first end of the frustum variant, and an essentially planar cap seals the second end of the frustum variant.
- the first end has broader dimensions than the second end.
- the cross-section at least one of the first end and second end can be oblong.
- the cross-section of both the first and second end can be non-circular. In some embodiments, the cross-section of both the first and second end can be oblong.
- the rupture disc is in electrical contact with the essentially planar cap, preferably through a weld.
- the weld connecting the pressure disc and the rupture disc ruptures when a gauge pressure between the discs is in a range of between about 4 kg/cm and about 9 kg/cm 2 , preferably in a range of between about 7 kg/cm and about 9 kg/cm .
- the rupture disc can define a depression, and the weld can be at the depression.
- the weld can be at least one spot weld, preferably two spot welds, with at least one of the spot welds including aluminum.
- the rupture disc can define at least one opening. At least one of the pressure disc and the rupture disc can include aluminum. In some embodiments, both the pressure disc and the rupture disc can include aluminum.
- the thickness of the cap can be in a range of between about 0.05 millimeter and about 0.5 millimeter, such as about 0.127 millimeter.
- the diameter of the cap can be in a range of between about 2 millimeters and about 8 millimeters.
- the height of the cap from the base can be in a range of between about 0.5 millimeter and about 1 millimeter, such as about 0.762 millimeter.
- the frustum variant can have an angle to a plane parallel to the base of the pressure disc in a range of between about 15 degrees and about 25 degrees.
- an electrically insulating ring can extend about the perimeter of the frustum variant and between the base of the pressure disc and the rupture disc.
- the base of the pressure disc can include at least one tab and the electrically insulating ring can define at least one opening, the tab and the opening being capable of alignment when the insulating ring and the base are concentric, wherein the tab can be maleably adjusted to secure the insulating ring to the pressure disc.
- the electrically insulating ring can define a groove about a perimeter of the insulating ring.
- These embodiments can further include a metal ring having tabs, whereby the metal ring can rest inside the groove and whereby the tabs can be maleably adjusted and secured to a metal surface on which the pressure disc is resting, thereby securing the insulating ring over the pressure disc.
- the thickness of the rupture disc proximate to the weld with the pressure disc can be less than the thickness of the pressure disc proximate to the weld, more preferably equal to or less than one-half of the thickness of the pressure disc proximate to the weld.
- the modular current interrupt device can be fabricated separately from the lithium ion battery, thereby significantly reducing the costs of fabrication of the battery and increasing the types of applications to which the modular CID can be applied.
- the modular CID includes a significantly increased surface area relative to typical conventional current interrupt devices for welding a tab from a cell jellyroll and, consequently, significantly increasing battery yield during production.
- the pressure disc does not need to include through-holes to allow passage of gas, thereby eliminating the likelihood of blockage of the hole during welding of a tab from a cell jellyroll.
- the modular current interrupt device of the invention can be universal in at least one orientation, such as by having a circular shape, thereby eliminating the need to orient the current interrupt device during assembly. The likelihood of error during fabrication and consequent rejection during quality checks is thereby significantly reduced.
- a beveled edge on the rupture disc in one embodiment, defines a channel and provides a means to mechanically secure the rupture disc to an electrically-insulating ring of the current interrupt device, thereby eliminating the need for the rupture disc to define through- holes to communicate gas pressure to the pressure disc.
- An advantage of an elongated, non-circular pressure disc is that within the envelope of any given prismatic cell design, it is possible to achieve lower activation or reversal pressures by using an elongated pressure disc (oblong, oval, etc.) compared to a circular pressure disc of the same material thickness.
- FIG. l is a cross-sectional view of one embodiment of a modular current interrupt device of the invention.
- FIGS. 2A and 2B are plan and cross sectional views, respectively, of an electrically-conductive rupture disc component of the modular current interrupt device of FIG. 1.
- FIGS. 3A and 3B are plan and cross sectional views, respectively, of an electrically-conductive pressure disc component of the modular current interrupt device of FIG. 1.
- FIGS. 4A, 4B and 4C are perspective, cross-sectional and plan views of one embodiment of an electrically-insulating ring component of the modular current interrupt device of FIG. 1.
- FIG. 5 is a partial cross-sectional view of the modular current interrupt device of FIG. 1, taken along line V-V.
- FIGS. 6 A and 6B are plan and cross-sectional views, respectively, of a seating element component of the modular current interrupt device of FIG. 1.
- FIGS. 7 A through 7D show steps in one method of the invention to fabricate one embodiment of the modular current interrupt device of the invention.
- FIGS. 8A, 8B and 8C are exterior, cross sectional, and interior views, respectively, of a lid of a prismatic battery cell showing a modular current interrupt device of the invention affixed to the lid.
- FIG. 9 is a cross sectional view of a prismatic battery cell of the invention, showing a modular current interrupt device of the invention, also in cross section, set in place in the lid.
- FIG. 10 is a plan view of an elongated, or oblong, pressure disc of the invention, having a frustum variant-type shape, shown next to a circular pressure disc having a frustum shape that is not a variant.
- FIG. 1 1 is a cross-sectional view of one embodiment of a CID of the invention.
- FIG. 12 shows one embodiment of a pressure disc of the CID of FIG. 11.
- the invention generally is directed to a modular current interrupt device for a battery, such as a lithium ion battery, and, particularly, a prismatic lithium ion battery.
- a battery such as a lithium ion battery, and, particularly, a prismatic lithium ion battery.
- the invention is a battery that includes the modular current interrupt device.
- the invention is a method of fabricating a modular current interrupt device.
- the "terminals" of the batteries of the invention mean the parts or surfaces of the batteries to which external electric circuits are connected.
- the phrases “electrically connected” or “in electrical communication” or “electrically contacted” mean certain parts are in communication with each other by flow of electrons through conductors, as opposed to electro- chemical communication which involves flow of ions, such as Li + , through electrolytes.
- FIG. 1 is a cross-sectional view of one embodiment of modular current interrupt device 10, and includes electrically-conductive rupture disc 12, electrically- conductive pressure disc 14, electrically-insulating ring 16, and seating element 18,
- electrically-conductive rupture disc 12 includes central recessed portions 1 1, 13, each of which, independently, has a depth in a range of between about 0.16mm and about 0.26mm, and a width in a range of between about 2.95mm and about 3.05mm.
- electrically-conductive rupture disc 240 can include a single central recessed portion 280.
- Electrically-conductive rupture disc 12, as shown in FIG. 2A is a polygon. Although shown having fourteen sides in FIG.
- electrically-conductive rupture disc 12 typically can have between about 10 and 20 sides 48. Sides 48 of electrically-conductive rupture disc 12 intersect and thereby define retention points 50.
- rupture disc 12 includes vent through-holes, not shown.
- Beveled edges 20, 22 of rupture disc 12 have an angle to a major plane of rupture disc 12 that is typically in a range of between about 40 degrees and 55 degrees. Preferably, the angle of beveled edges 20, 22 is in a range of between about 45° and about 49°, and most preferably is about 47°.
- rupture disc 12 has a major diameter D in a range between about 6mm and about 16mm and a thickness T in a range between about 0.3mm and 0.7mm.
- rupture disc 12 has a diameter of about 1 lmm and a thickness of about 0.5mm.
- the thickness of rupture disc 12 at recessed portions 1 1, 13 generally is in a range of between about 0.065mm and preferably about 0,085mm.
- Rupture disc 12 is fabricated of a suitable material. Examples of suitable materials include aluminum, nickel and copper. Examples of suitable materials include Aluminum 3003 series, such as Aluminum 3003 H-O or H-14 series, and preferably H-14 series.
- electrically-conductive pressure disc 14 is attached to electrically-conductive rupture disc 12 at weld points 24, 26.
- electrically-conductive pressure disc 14 can be connected to electrically-conductive rupture disc 12 without any weld points, a single weld point, or three or more weld points.
- the weld points are spot welds.
- the spot welds are separated from each other.
- the spot welds include aluminum.
- electrically- conductive pressure disc 14 preferably includes frustum 28.
- Frustum or frustoconical component 28 has first end 30 and second end 32.
- First end 30 has a broader diameter than second end 32
- Electrically-conductive pressure disc 14 also includes base 34 extending radially from a perimeter of first end 30 of frustum 28.
- Cap 36 seals second end 32 of frustum 28.
- frustum means the basal wall part (excluding the bottom and top ends) of a solid right circular cone (i.e., solid generated by rotating a right triangle about one of its legs) the top of which is cut off.
- cap 36 is essentially planar.
- frustum 28 can be a frustrum variant, such as where a cross-section of first end 30 or second 32 is each, independently, non-circular.
- the cross-section of each of first and 30 and second and 32 is oblong, as indicated at Fig. 10 with reference to pressure disc 120.
- the term "essentially planar or cap” means a surface that sufficiently resembles a plane so as to potentially contact another planar surface randomly at one or more points and to which the surface can be fused by a suitable means, such as by spot welding.
- cap 36 in some embodiments, despite deformation caused by fabrication of pressure disc 14 or by assembly to form modular current interrupt device 10, shown in FIG. 1 (e.g., by welding electrically-conductive rupture disc 12 to electrically-conductive pressure disc 14), cap 36 nevertheless is considered to be essentially planar.
- a forming pin deforms both cap 36 on pressure disc 14 and coined feature 11 on rupture disc 12 at the same time.
- pressure disc 14 is attached to rupture disc 12 to form an electrically conductive pathway.
- pressure disc 14 and rupture disc 12 are spot welded together with the number of weld spot locations in the range of between 1 and about 6, such as 2 weld spots.
- laser welding is used.
- the laser welding equipment is set-up to hit each weld spot in rapid succession with multiple repeated laser pulses. The energy of each of the repeated laser pulses is adjusted so that the combined energy of all repeated laser pulses in one weld spot is sufficient to locally melt the aluminum in pressure disc 14 and rupture disc 12, thereby binding them metallically together in a weld spot.
- the advantage of using multiple repeated laser pulses is that the variation in the total laser energy provided to each weld spot is significantly reduced, thereby creating less variation in the spot weld strength, compared to using a single laser pulse of higher power.
- cap 36 and/or base 34 each, independently, has a thickness of material (indicated with reference character “d” in Figure 3B) in a range between or about 0.05 mm and about 0.5 mm such as between about 0.05 mm and about 0.3 mm, between about 0.05 mm and 0,2 mm, between about 0.05 mm and about 0.15 mm (e.g., about 0.127 mm) or about 5 milli-inches.
- the diameter of cap 36 (indicated with reference character "b" in FIGS.
- 3 A and 3B is in a range of between about 2 mm and about 10 mm, more preferably between 5 mm and about 10 mm, even more preferably between about 5 mm and about 10 mm even more preferably between about 5 mm and about 8 mm (e.g., between about 0.20 inches and 0.25 inches) such as about 5.5 mm (or about 0.215 inches).
- the surface of cap 36 is elevated from peripheral base 34.
- the height of cap 36 from base 34 is in a range of between about 0.5 millimeter and about 1 millimeter, more preferably between about 0.55 millimeter and about 0.65 millimeter, such as about 0.596 millimeter (or about 0.024 inch).
- frustum 28 has an angle relative to a plane parallel to base 34 in a range of between about 15 degrees and about 25 degrees, such as between about 18 degrees and about 23 degrees, or between about 19 degrees and about 21 degrees. More preferably, frustum 28 has an angle of about 21 degrees relative to a plane parallel to base 34.
- frustum 28 has a diameter ratio of first end 30 to second end 32 (i.e., ratio of "b" to "a” in FIG. 3B) in a range of between about 1 : 1.20 and about 1 :1.35, such as between about 1 : 1.23 and about 1 : 1.28.
- electrically-conductive rupture disc 12 and electrically-conductive pressure disc 14 separate when an internal gauge pressure applied to a surface of electrically-conductive pressure disc 14 contacting electrically-conductive rupture disc 12 is in a range of between about 4 kg/cm 2 and
- modular current interrupt device 10 0 O O O about 5 kg/cm and about 9 kg/cm or between about 7 kg/cm and about 9 kg/cm .
- activation of modular current interrupt device 10 means that current flow between electrically-conductive rupture disc 12 and electrically-conductive pressure disc 14 is interrupted.
- electrically-conductive pressure disc 14 separates from electrically-conductive rupture disc 12
- the integrity of electrically-conductive pressure disc 14 is maintained, whereby pressure disc 14 does not fracture or otherwise permit gas to flow from one side of pressure disc 14 to another side of pressure disc 14.
- separation of pressure disc 14 from rupture disc 12 causes fracture of any spot welds electrically connecting pressure disc 14 to rupture disc 12,
- Pressure disc 14 can be formed of a suitable metal such as aluminum, copper and nickel.
- suitable aluminum is Aluminum 3003 series, such as Aluminum 3003 H-O or H-14 series.
- the pressure disc 14 includes aluminum and, more preferably, consists essentially of aluminum.
- Electrically-insulating ring 16 partitions a perimeter of rupture disc 12 from a perimeter of pressure disc 14.
- electrically-insulating ring 16 includes base 38 and rim 40.
- rim 40 is spaced from perimeter of base 38 by a distance "b" in a range between about 0.40 mm and about 0.55mm.
- Rim 40 typically has a height "h” in a range of between about 0.80mm and about 0.90mm.
- Lip 44 extends from rim 40 and overlaps electrically-conductive rupture disc 12, In one embodiment, lip 44 contacts rupture disc 12 to thereby cause an interference fit between base 38 and rupture disc 12.
- electrically-insulating ring 16 defines channels 46 at base 38.
- At least one of channels 46 has a major axis that is essentially normal to a tangent of a circle defined by ring 16.
- suitable materials of electrically-insulating ring 16 include polypropylene, such as high- density polypropylene, and perfluoroalkoxy copolymer resin.
- points 50 of rupture disc 12 typically are in interfering relation with rim 40 of electrically-insulating ring 16.
- Sides 48 of electrically-conductive rupture disc 12 and rim 40 of electrically-insulating ring 16 define conduits 42 that provide fluid communication of gas pressure from one side of rupture disc 12 to the other side of rupture disc 12.
- Channels 46 of ring 16 also provide fluid communication between the major surfaces of rupture disc 12.
- Seating element, or seating cup, 18 overlays pressure disc 14.
- Crimp 58 at periphery of seating element 18 secures pressure disc 14 to electrically-insulating ring 16.
- seating element 18 can be secured to pressure disc 14 by welds (not shown) where seating element 18 contacts electrically-conductive pressure disc 14.
- the diameter of opening 56 is in a range of between about 2mm and about 4mm.
- Seating element 18 is fabricated of a suitable material, such as aluminum, nickel and copper.
- seating element 18 is formed of metal and is electrically connected to pressure disc 14.
- seating element 18 includes aluminum, and more preferably consists essentially of aluminum.
- seating element 18 can be formed of an electrically insulating material, such as polypropylene.
- the thickness of the material employed to form seating element 18 is in a range of between about 0.3mm and about 0.5mm.
- a method of fabricating a modular current interrupt device of the invention includes combining electrically-conductive pressure disc 14 with seating element 18, and combining electrically-conductive rupture disc 12 with electrically-insulating ring 16.
- the combined electrically-conductive pressure disc 14 and seating element 18, and combined electrically-conductive rupture disc 12 and electrically-insulating ring 16, are then secured to one another by mechanically or by other means joining the electrically-conductive rupture disc 12 and electrically-conductive pressure disc 14 by a suitable method, such as by laser or resistance spot welding.
- the edges of seating element 18 can be crimped around the edges of pressure disc 14 and insulating ring 16.
- FIGS. 7A through 7D pressure disc 14 and seating element 18 are combined, as shown in FIG.
- a single seam is formed by a suitable method, such as crimping, as shown in FIG.7B.
- a suitable lining compound such as a sealing material (e.g., an asphaltic-based sealing material) that is electrolyte-resistant, as is known in the art, can be placed between joining surfaces of pressure disc 14 and seating element 18.
- a double seam as a hermetic seal, is then formed.
- Insulating ring 16 is then placed at pressure disc 14, and pressure disc 14 and seating element 18 are then crimped again to clamp down insulating ring 14.
- pressure disc 12 is then put into place, as shown in FIG. 1, and spot welded to pressure disc 14, as described above.
- electrically-conductive pressure disc 14 and electrically- conductive rupture disc 12 are made of substantially the same metals.
- substantially the same metals means metals that have substantially the same chemical and electrochemical stability at a given voltage, e.g., the operating voltage of a battery.
- at least one of electrically-conductive rupture disc 12 and electrically-conductive pressure disc 14 includes aluminum, such as Aluminum 3003 series.
- electrically-conductive pressure disc 14 includes aluminum which is softer than that of electrically-conductive rupture disc 12.
- electrically- conductive pressure disc 14 and electrically-conductive rupture disc 12 both include aluminum.
- rupture disc 12 is formed of Aluminum 3003 H- 14 series and pressure disc 14 is formed of Aluminum 3003 H-O series.
- Pressure disc 12 and rupture disc 14 can be made by any suitable method known in the art, such as, for example, stamping, coining, and/or milling techniques.
- FIGS. 8A, 8B and 8C show, respectively, exterior plan, cross-sectional and interior plan views of a lid assembly of a battery that includes a modular current interrupt device of the invention. As can be seen in FIGS. 8A, 8B and 8C, current interrupt device 10 is set within through-opening 62 defined by Hd 60 of a battery. The majority of modular current interrupt device 10 is located within the battery while raised portion 54 of seating element 18 resides within through-opening 62 of lid 60.
- Seating element 18 is fixed to lid 60 by a suitable method, such as by an interference fit, welding, crimping, riveting, etc.
- seating element 18 and lid 60 are welded to each other. Any suitable welding technique known in the art can be used.
- seating element 18 and lid 60 are hermetically joined.
- a laser welding technique is employed in the invention. More preferably, a circumferential laser welding technique is employed to hermetically join seating element 18 and lid 60, for example, either by means of seam welding at the circumferential interface between two parts or by means of penetration welding at base 62 of seating element 18.
- the welding is circumferentially placed around the middle of base 52 or the edge of base 52.
- a temperature of seating element 18 is controlled so as not to exceed the melting point of a surface of seating element 18 opposite the weld.
- a temperature control can be obtained using any suitable cooling method known in the art
- lid 60 is fabricated out of substantially the same material as that of seating element 18, such as Aluminum 3003 H-O or H- 14 series.
- FIG. 8 A which is a plan view of the outside of lid 60 of a battery, raised portion 54 of seating element 18 is visible and essentially circular in configuration.
- seating element 18, as well as the remainder of lid 60 and a can of a battery to which lid 60 is electrically connected serves as a positive terminal
- feed-through assembly 64 also shown in FIG. 8A through 8C, serves as the negative terminal of the battery and is electrically insulated by component 66 from the remainder of lid 60, from modular current interrupt device 10 and from a can of a battery to which lid 60 is electrically connected
- FIG. 9 shows a cross-sectional view of a battery 70 of the invention that includes lid 60, in which modular current interrupt device 10 is seated.
- Tab 72 connects one electrode, preferably a positive electrode, to rupture disc 12.
- Tab 72 can be joined to rupture disc 12 by a suitable method, such as laser or resistance spot welding.
- Tab 74 connects the other electrode to feed-through assembly 64, also by a suitable method, such a laser or resistance spot welding.
- the electrically conductive components of modular current interrupt device 10 can be formed of materials other than aluminum such as nickel- plated iron, particularly when the current interrupt device 10 is electrically connected to the anode of the battery, rather than to the cathode.
- a pressure disc of non-circular shape provides a larger surface area as compared to a circular pressure disc that fits in the same size (non circular) envelope.
- the larger available area allows for a lower activation pressure compared to a circular pressure disc that fits in the same rectangular envelope base.
- the space available for the pressure disc decreases.
- the maximum size of a circular pressure disc is so small that the force due to the pressure is insufficient to actuate the pressure mechanism in the preferred pressure range.
- Making the pressure disc material very thin could bring the reversal pressure down to the preferred range.
- using very thin material weakens the structural integrity of the pressure disc and increases the risk of punctures and leaks.
- the elongated, or oblong, disc 120 of the invention is shown in Figure 10, and is shown in comparison to a pressure disc 80 having a circular cross-section at both first and second ends of a frustum.
- Table 1 shows the results of tests of an elongated pressure disc of the invention.
- the elongated, or oblong, shape of the disc increases the area available for the pressure force as compared to a circular pressure disc that a given prismatic cell could accommodate, therefore improving the sensitivity of the pressure disc and allowing operation with a thin form factor
- the CID of the battery of the invention which employs a pressure disc and a rupture disc that is in electrical communication with, and pressure (i.e., fluid such as gas) communication with, the pressure disc and with
- the battery can of the battery, activates at an internal gauge pressure in a range of, for example, between about 4 kg/cm 2 and about 9 kg/cm 2 , such as between about 5 kg/cm 2 and about 9 kg/cm 2 or between about 7 kg/cm 2 and about 9 kg/cm 2 .
- the pressure disc includes a cone- or dome-shaped part. More preferably, at least a portion of the top (or cap) of the cone- or dome-shaped part is essentially planar.
- the pressure disc and the rupture disc are in direct contact with each other at a portion of the essentially planar cap. More preferably, the pressure disc includes a frustum having an essentially planar cap.
- activation of the CID means that current flow of an electronic device through the CID is interrupted.
- the CID of the invention includes a pressure disc and a rupture disc in electrical communication with each other (e.g., by welding, crimping, riveting, etc.).
- activation of the CID means that the electrical communication between the pressure disc and the rupture disc is interrupted.
- the rupture disc separates from (e.g., deforms away or is detached from) the pressure disc, no rupture occurs in the pressure disc.
- FIG. 11 shows a cross-section of one specific embodiment of the CID of the invention.
- CID 100 shown in FIG. 10 includes pressure disc 120 and rupture disc 240.
- Pressure disc 120 includes frustum variant 140 (also referred to as frustum 140) that includes first end 160 and second end 180.
- Frustum variant has a cross- sectional shape (such as that taken along line I-I with respect to second end 180) that is non-circular, such as an elongated, or oblong shape, shown in FIG. 10, at at least one of first end 160 or second end 180.
- First end 160 has broader dimensions than second end 180.
- Pressure disc 120 also includes base 200 extending radially from a perimeter of first end 160 of frustum 140.
- frustum variant means the basal wall part (excluding the bottom and top ends) of a solid right non-circular cone which lies between two parallel planes cutting the cone.
- the frustum variant would be a right circular cone, but for the fact that the base or the cross- section of the portion of the cone that has been truncated, is not circular, but rather, elongated, or oblong, as shown in the left-hand portion of FIG.10, or some other non-circular shape.
- the length and width of the base of the elongated cone can have a ratio in a range of between about 1 :1.3 and about 1 :2, preferably about 1 :1.5, as shown in Fig. 10.
- flat cap 220 and/or base 200 has a thickness (indicated with reference character "d" in FIG. 12) in a range of between about 0.05 millimeters and about 0.5 millimeters, such as between about 0.05 millimeters and about 0.3 millimeters, between about 0.05 millimeters and 0.2 millimeters, between about 0,05 millimeters and about 0.15 millimeters (e.g., about 0.127 millimeter (or about 5 milli-inch)).
- the narrowest dimension of flat cap 220 is in a range of between about 1 millimeters and about 10 millimeters, more preferably between 2 millimeters and about 10 millimeters, even more preferably between about 2 millimeters and 6 millimeters, such as about 3 millimeters.
- the height of essentially planar cap 220 from base 200 is in a range of between about 0.5 millimeter and about 1 millimeter, more preferably between about 0.6 millimeter and about 0.8 millimeter, such as about 0.762 millimeter (or about 0.315 inch).
- frustum 140 has an angle relative to a plane parallel to base 200 in a range of between about 15 degrees and about 25 degrees, such as between about 18 degrees and about 23 degrees, or between about 19 degrees and about 21 degrees. More preferably, frustum 140 has an angle of about 21 degrees relative to a plane parallel to base 20.
- frustum 140 has a diameter ratio of first end 160 to second end 180 (i.e., ratio of "b" to "a” in FIG. 12) in a range of between about 1 : 1.20 and about 1 : 1.35, such as between about 1 : 1.23 and about 1 : 1.28.
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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)
- Connection Of Batteries Or Terminals (AREA)
- Gas Exhaust Devices For Batteries (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US20646109P | 2009-01-30 | 2009-01-30 | |
US16658009P | 2009-04-03 | 2009-04-03 | |
PCT/US2010/022327 WO2010088332A1 (en) | 2009-01-30 | 2010-01-28 | Modular cid assembly for a lithium ion battery |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2384519A1 true EP2384519A1 (de) | 2011-11-09 |
Family
ID=41818659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10702959A Withdrawn EP2384519A1 (de) | 2009-01-30 | 2010-01-28 | Modulare cid-anordnung für lithium-ionen-akkumulator |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2384519A1 (de) |
JP (1) | JP2012516545A (de) |
CN (1) | CN102292843A (de) |
TW (1) | TWI499150B (de) |
WO (1) | WO2010088332A1 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008002487A2 (en) | 2006-06-27 | 2008-01-03 | Boston-Power, Inc. | Integrated current-interrupt device for lithium-ion cells |
EP2162935A1 (de) | 2007-06-22 | 2010-03-17 | Boston-Power, Inc. | Cid-retentionseinrichtung für eine li-ionen-zelle |
US8642195B2 (en) | 2008-12-19 | 2014-02-04 | Boston-Power, Inc. | Modular CID assembly for a lithium ion battery |
US20130143110A1 (en) * | 2011-12-01 | 2013-06-06 | Roger Neil Bull | System and method for enclosing an energy storage cell |
WO2014022445A1 (en) * | 2012-08-01 | 2014-02-06 | Enerdel, Inc. | Modular energy storage system |
CN105870366B (zh) * | 2016-06-07 | 2019-03-15 | 宁德时代新能源科技股份有限公司 | 动力电池顶盖及动力电池 |
CN108428822B (zh) * | 2017-08-30 | 2023-10-20 | 宁德时代新能源科技股份有限公司 | 二次电池的顶盖组件以及二次电池 |
CN207818642U (zh) * | 2017-12-22 | 2018-09-04 | 比亚迪股份有限公司 | 电池盖板组件、单体电池、电池模组、动力电池及电动汽车 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1132983A1 (de) * | 2000-03-09 | 2001-09-12 | Sanyo Electric Co., Ltd. | Batterie-Sicherheitsventil und Herstellverfahren dafür |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69527735T2 (de) * | 1994-03-03 | 2002-12-05 | Japan Storage Battery Co Ltd | Sicherheitsanordnung für Batterie |
JP3349601B2 (ja) * | 1994-10-14 | 2002-11-25 | 日立マクセル株式会社 | 防爆形密閉電池 |
FR2756421B1 (fr) * | 1996-11-28 | 1998-12-24 | Accumulateurs Fixes | Generateur electrochimique etanche equipe d'une borne coupe circuit |
JP3646442B2 (ja) * | 1996-12-05 | 2005-05-11 | ソニー株式会社 | 非水電解液電池 |
US6204635B1 (en) * | 1998-05-22 | 2001-03-20 | Texas Instruments Incorporated | Current interrupt apparatus particularly adapted for use with prismatic electrochemical cells |
JP4269356B2 (ja) * | 1998-07-30 | 2009-05-27 | パナソニック株式会社 | 密閉型電池用防爆封口板 |
WO2007149102A1 (en) * | 2006-06-23 | 2007-12-27 | Boston-Power, Inc. | Lithium battery with external positive thermal coefficient layer |
WO2008002487A2 (en) * | 2006-06-27 | 2008-01-03 | Boston-Power, Inc. | Integrated current-interrupt device for lithium-ion cells |
KR101058293B1 (ko) * | 2006-10-23 | 2011-08-22 | 주식회사 엘지화학 | 우수한 안전성을 발휘하는 전기화학소자 |
WO2008069476A1 (en) * | 2006-12-05 | 2008-06-12 | Moon, Seung-Ja | Cylindrical secondary battery and method of manufacturing the same |
EP2162935A1 (de) * | 2007-06-22 | 2010-03-17 | Boston-Power, Inc. | Cid-retentionseinrichtung für eine li-ionen-zelle |
-
2010
- 2010-01-28 EP EP10702959A patent/EP2384519A1/de not_active Withdrawn
- 2010-01-28 WO PCT/US2010/022327 patent/WO2010088332A1/en active Application Filing
- 2010-01-28 JP JP2011548276A patent/JP2012516545A/ja active Pending
- 2010-01-28 TW TW099102387A patent/TWI499150B/zh not_active IP Right Cessation
- 2010-01-28 CN CN2010800050710A patent/CN102292843A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1132983A1 (de) * | 2000-03-09 | 2001-09-12 | Sanyo Electric Co., Ltd. | Batterie-Sicherheitsventil und Herstellverfahren dafür |
Also Published As
Publication number | Publication date |
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TW201032433A (en) | 2010-09-01 |
TWI499150B (zh) | 2015-09-01 |
WO2010088332A1 (en) | 2010-08-05 |
JP2012516545A (ja) | 2012-07-19 |
CN102292843A (zh) | 2011-12-21 |
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