Patent Application
20110008654
The present invention relates to a cap assembly of improved safety and a cylindrical secondary battery including the same, and, more particularly, to a cap assembly loaded on an open upper end of a cylindrical container of a battery in which an electrode assembly is mounted in the cylindrical container, the cap assembly including a safety vent having a predetermined notch configured to rupture by high-pressure gas generated in the battery, a current interruptive device coupled to a bottom of the safety vent by welding for interrupting current when internal pressure of the battery increases, and a current interruptive device gasket for surrounding an outer circumference of the current interruptive device, wherein the current interruptive device includes two or more through holes for gas discharge, the through holes being formed such that the sum of areas of the through holes is equal to 20% to 50% of an entire area of the current interruptive device.
As mobile devices have been increasingly developed, and the demand of such mobile devices has increased, the demand of secondary batteries has also sharply increased as an energy source for the mobile devices. Among such secondary batteries is a lithium secondary battery having high energy density and high discharge voltage, into which much research has been carried out and which is now commercially and widely used.
Depending upon the shape of a battery case, a secondary battery may be classified as a cylindrical battery having an electrode assembly mounted in a cylindrical metal container, a prismatic battery having an electrode assembly mounted in a prismatic metal container, or a pouch-shaped battery having an electrode assembly mounted in a pouch-shaped case formed of an aluminum laminate sheet. The cylindrical battery has advantages in that the cylindrical battery has relatively large capacity and is structurally stable.
The electrode assembly mounted in the battery case is a power generating element, having a cathode/separator/anode stack structure, which can be charged and discharged. The electrode assembly may be classified as a jelly roll type electrode assembly constructed in a structure in which a long sheet type cathode and a long sheet type anode, to which active materials are applied, are wound while a separator is disposed between the cathode and the anode or a stacked type electrode assembly constructed in a structure in which pluralities of cathodes and anodes having a predetermined size are sequentially stacked while separators are disposed respectively between the cathodes and the anodes. The jelly roll type electrode assembly has advantages in that the jelly roll type electrode assembly is easy to manufacture and has high energy density per weight.
Referring to
The electrode assembly 120 is constructed in a structure in which a cathode 121 and an anode 122 are wound in a circle while a separator 123 is interposed between the cathode 121 and the anode 122. A cylindrical center pin 150 is disposed at the center of the winding (the center of the jelly roll). The center pin 150 is generally made of a metal material to exhibit predetermined strength. The center pin 150 is constructed in a hollow cylindrical structure formed by rolling a metal sheet. The center pin 150 serves to fix and support the electrode assembly. In addition, the center pin 150 serves as a passage to discharge gas generated by internal reaction of the secondary battery when charging, discharging, and operating the secondary battery.
Meanwhile, a lithium secondary battery has a disadvantage in that the lithium secondary battery has low safety. For example, when the secondary battery is overcharged to approximately 4.5 V or more, a cathode active material is decomposed, dendritic growth of lithium metal occurs at an anode, and an anode active material is decomposed. At this time, heat is generated from the secondary battery, with the result that the above-mentioned decompositions and several sub decompositions rapidly progress, and, eventually, the secondary battery may catch fire and explode.
In order to solve the above-mentioned problems, therefore, a general cylindrical secondary battery includes a current interruptive device (CID) and a safety vent mounted between the electrode assembly and the top cap for interrupting current and releasing internal pressure when the operation of the secondary battery is abnormal.
The above-described components will be described hereinafter with reference to
Referring to these drawings, a top cap 10 protrudes to form a cathode terminal. The top cap 10 has exhaust ports. Below the top cap 10 are sequentially disposed a positive temperature coefficient (PTC) element 20 for interrupting current through the great increase of battery resistance when the interior temperature of the battery increases, a safety vent 30 configured to have a downward depressed shape in a normal state and to protrude and rupture for discharging gas when the interior pressure of the battery increases, and a connection plate 50 coupled to the safety vent 30 at one side of the upper end thereof and connected to a cathode of an electrode assembly 40 at one side of the lower end thereof.
In normal operating conditions, therefore, the cathode of the electrode assembly 40 is connected to the top cap 10 via a lead 42, the connection plate 50, the safety vent 30, and the PTC element 20 to achieve electric conduction.
However, when gas is generated from the electrode assembly 40 due to various causes, such as overcharging, with the result that the internal pressure of the battery increases, as shown in
However, this operating process is absolutely dependent on the amount of gas generated from the electrode assembly or the amount of gas discharged from the battery. If the amount of generated gas or the amount of discharged gas is not sufficient or does not increase to a predetermined level within a short period of time, a short circuit may occur late, and a thermal runaway phenomenon may occur due to continuous electric conduction of the electrode assembly. The thermal runaway phenomenon occurs or is further accelerated when the battery is in continuous electric conduction, with the result that a possibility of the battery catching fire or exploding greatly increases. Consequently, the safety of the battery is seriously threatened. Furthermore, there have continuously occurred ignition accidents of laptop computers in recent years, and therefore, the importance of the safety of the battery is being further emphasized.
Therefore, there is a high necessity for development of a cap assembly that is capable of rapidly discharging gas out of a battery when the gas is generated in the battery due to various causes, such as overcharging, with the result that the internal pressure of the battery increases.
Therefore, the present invention has been made to solve the above problems, and other technical problems that have yet to be resolved.
Specifically, it is an object of the present invention to provide a cap assembly of improved safety that is capable of rapidly pressurized gas out of a battery.
It is another object of the present invention to provide a lithium secondary battery of improved safety achieved by using a cap assembly of improved safety.
In accordance with one aspect of the present invention, the above and other objects can be accomplished by the provision of a cap assembly loaded on an open upper end of a cylindrical container of a battery in which an electrode assembly is mounted in the cylindrical container, the cap assembly including a safety vent having a predetermined notch configured to rupture by high-pressure gas generated in the battery, a current interruptive device coupled to the bottom of the safety vent by welding for interrupting current when internal pressure of the battery increases, and a current interruptive device gasket for surrounding the outer circumference of the current interruptive device, wherein the current interruptive device includes two or more through holes for gas discharge, the through holes being formed such that the sum of areas of the through holes is equal to 20% to 50% of the entire area of the current interruptive device.
The current interruptive device may be configured to rupture for interrupting current when the interior pressure of the battery increases. The current interruptive device may be constructed in a structure in which the current interruptive device is provided at a center thereof with a protrusion configured to protrude upward such that the protrusion is fixed to the bottom of a depression of the safety vent by welding, and a cathode lead connected to a cathode of a jelly roll is electrically connected to the current interruptive device via the bottom of the depression excluding the protrusion.
Since the current interruptive device is coupled to the safety vent as described above, the connection between the current interruptive device and the cathode ruptures, when the shape of the safety vent is inversed, thereby interrupting current. In a concrete example, the protrusion may be provided at the outer circumference thereof with a notch. When the shape of the safety vent is inversed, the notch ruptures, with the result that the separation between the current interruptive device and the cathode may be easily achieved in a state in which the protrusion is coupled to the safety vent.
Also, the current interruptive device may be provided with two or more through holes through which gas flows upward. Gas in the battery raises through the through holes to inverse the shape of the safety vent.
However, the inventors of the present application have experimentally found that, when the sum of areas of the through holes formed at the current interruptive device is less than 20% of the entire area of the current interruptive device, the battery more easily catches fire or explodes due to high pressure generated in the battery. This may be because the amount of gas passing through the through holes is small, and therefore, current interruption is not effectively achieved or because upward flow of gas is interrupted or changed, and therefore, time necessary to interrupt current is increased. On the other hand, when the size of the through holes is excessively large, it is difficult to secure predetermined strength, and, parts may be twisted during the manufacture of the current interruptive device, which is not preferable.
In the cap assembly according to the present invention, the current interruptive device includes two or more through holes for gas discharge, and the through holes are formed such that the sum of areas of the through holes is equal to 20% to 50%, more preferably 30% to 40%, of the entire area of the current interruptive device. As a result, it is possible to increase the amount of upward-flowing gas (the amount of discharged gas) and to achieve rapid upward flow (discharge) of the gas.
Consequently, when gas is generated in the battery due to various causes, such as overcharging, with the result that the internal pressure of the battery increases, the gas is rapidly discharged out of the battery by current interruption and rupture of the safety vent, thereby securing safety of the battery.
The through holes may be formed in a shape of an arc such that the through holes are radially symmetrical about a center of the current interruptive device. When the through holes are radially symmetrical as described above, excessive discharge of gas in one direction is prevented, and the strength of the current interruptive device is secured.
The number of the through holes is not particularly restricted. Preferably, the number of the through holes is 2 to 4.
In a preferred example, three through holes may be arranged at regular intervals such that the through holes each have an arc shape corresponding to an angle of 50 to 80 degrees about the center of the current interruptive device.
Meanwhile, the protrusion may be formed in a structure in which three to five through slits are formed on a concentric circle of the protrusion, and bridges are formed on the concentric circle of the protrusion for interconnecting the through slits, each of the bridges having a notch. In this case, the through slits may be arranged at regular intervals such that the through slits correspond to the through holes, preferably the through slits each have an arc shape corresponding to an angle of 40 to 55 degrees about the center of the current interruptive device.
The safety vent is a device that discharges gas out of the battery, when the internal pressure of the battery increases, to secure safety of the battery. For example, when gas is generated in the battery, with the result that the internal pressure of the battery reaches a critical value, the safety vent ruptures, and therefore, gas passes through the rupture of the safety vent and is then discharged out of the battery through one or more exhaust ports formed in a top cap.
The safety vent may be provided at a center thereof with a depression configured to be depressed downward. In this structure, the depression of the safety vent is inversed, i.e., the downward depressed shape of the center of the safety vent is inversed into the upward protruding shape of the center of the safety vent, when the internal pressure of the battery increases, with the result that the safety vent is separated from the current interruptive device, thereby interrupting electric connection.
The operation of the safety vent is as follows. Gas generated in the battery passes through the through holes of the current interruptive device to apply upward pressure to the safety vent. When the upward pressure reaches a predetermined pressure (hereinafter, referred to as ‘first critical pressure’), the shape of the downward depression of the safety vent is inversed, with the result that the protrusion fixed to the depression is separated from the current interruptive device to interrupt electric conduction from the current interruptive device to the safety vent.
The depression may include an upper bent portion and a lower bent portion. A first notch may be formed at the upper bent portion. In the related art, a structure in which only the lower bent portion is cut off has been proposed. However, the lower bent portion is not suitable for effective gas discharge because the lower bent portion has a small area. According to the present invention, on the other hand, a notch configured to rupture is formed at the upper bent portion, with the result that the cutoff area is relatively large, and therefore, it is possible to rapidly discharge a large amount of gas.
When the internal pressure of the battery continuously increases in spite of the current interruption achieved by the safety vent, with the result that the internal pressure of the battery reaches another predetermined pressure (hereinafter, referred to as ‘second critical pressure’), the first notch is cut off. Consequently, pressurized gas in the battery is discharged out of the battery through the exhaust ports of the top cap.
Meanwhile, the first notch may be configured in a shape of an open curve, one side of which is open to prevent the entirety of the upper bent portion from being separated from the remaining portion of the safety vent. That is, the one-side open region serves as a bridge between the depression and the remaining portion of the safety vent.
The size of the first notch is not particularly restricted. Preferably, the first notch has a size corresponding to that of an imaginary circle formed by linking centers of the through holes formed in the current interruptive device such that gas flowing upward from the current interruptive device directly applies pressure to the first notch.
Also, as previously described, the open region of the first notch may have a size to prevent the depression from being completely cut off when the first notch is cut off. The open region of the first notch may have an arc length corresponding to an angle of preferably 20 to 50 degrees, more preferably 25 to 40 degrees, about the center of the safety vent.
In a preferred example, second notches may be formed at the lower bent portion of the safety vent. Preferably, the second notches are configured in the shape of open curves, opposite ends of which are open such that only the upper bent portion is cut off when the internal pressure of the battery increases. In the structure in which the opposite ends are open, the cutoff of the lower bent portion is restrained, and opening due to the cutoff of the upper bent portion is achieved, when the internal pressure of the battery increases.
Preferably, the open opposite sides of the second notch are not aligned with the open region of the first notch. In a more preferred example, the open opposite sides of the second notch may be located approximately at a right angle to the open region of the first notch.
In a preferred example, the first notch may have a greater depth than the second notches such that the first notch ruptures (is cut off) before the second notches.
The material for the safety vent is not particularly restricted. Preferably, the safety vent is formed of an aluminum sheet having a thickness of 0.15 to 0.4 mm such that the safety vent ruptures (is cut off) when the internal pressure of the battery reaches a critical value.
The current interruptive device gasket is configured to surround the outer circumference of the current interruptive device. In a preferred example, the current interruptive device gasket may have an opening formed in the center thereof. Since it is preferable to configure the flow path of pressurized gas in a straight line such that the upward flow of the gas is efficiently achieved, the central opening of the current interruptive device gasket may be configured in a shape not to cover the through holes of the current interruptive device.
In the related art, the gasket is formed into a shape to partially cover the through holes of the current interruptive device. Therefore, the flow of high-pressure gas, having passed through the through holes, is disturbed by the gasket, with the result that the amount of discharged gas is reduced, and the flow path of gas is changed, whereby it is difficult to achieve prompt operation of the safety vent. In the structure in which the gasket does not cover the through holes as previously described, on the other hand, the entirety of high-pressure gas, having passed through the through holes, reaches directly to the safety vent, thereby further securing safety of the battery.
In a preferred example, the through holes of the current interruptive device, the opening of the current interruptive device gasket, and the notch of the safety vent may be aligned with one another in a straight line.
Until high-pressure gas generated in the battery reaches the notch of the safety vent through the through holes of the current interruptive device and the opening of the current interruptive device gasket, the gas flow path is maintained in a straight line, with the result that the high-pressure gas flows upward intensively and rapidly. Consequently, the prompt operation of the safety vent is achieved, thereby securing safety of the battery.
According to circumstances, the cap assembly according to the present invention may further include a positive temperature coefficient (PTC) element for interrupting current through the great increase of battery resistance when the interior temperature of the battery increases.
The cap assembly may be constructed in a structure in which the current interruptive device, the current interruptive device gasket, the safety vent, the PTC element, and the top cap having one or more exhaust ports are stacked. Also, a gasket may be further mounted to the outer circumference of the stacked structure. The PTC element may be disposed between the top cap and the safety vent in a tight contact state.
In accordance with another aspect of the present invention, there is provided a cylindrical battery including the cap assembly with the above-stated construction and an electrode assembly (jelly roll) of a cathode/separator/anode structure. The cylindrical battery is manufactured by inserting the jelly roll into a cylindrical container, injecting an electrolyte into the cylindrical container, and coupling a top cap 140 having an electrode terminal to the upper end, which is open, of the cylindrical container.
In a preferred example, the cylindrical battery may further include a disc-shaped insulating member loaded on the upper end of the jelly roll. The disc-shaped insulating member may be provided at the center thereof with an opening for gas discharge and electrode terminal connection. Also, the disc-shaped insulating member may be provided around the opening with at least one through hole.
In this case, it is preferable for the at least one through hole of the disc-shaped insulating member to have a size sufficient to be aligned with the opening of the current interruptive device gasket and the through holes of the current interruptive device in a straight line such that the at least one through hole of the disc-shaped insulating member communicates with the opening of the current interruptive device gasket and the through holes of the current interruptive device. For example, the at least one through hole may have a size equivalent to 20% to 50% of the area of the disc-shaped insulating member.
The material for the insulating member is not particularly restricted as long as the insulating member is formed of an insulative material. For example, the insulating member may be formed of a polypropylene resin. The high-strength polypropylene resin may be particularly preferably used since the polypropylene resin exhibits a high mechanical strength to thickness ratio, and therefore, the polypropylene resin prevents movement and short circuit of the jelly roll when strong external impact is applied to the battery.
The jelly roll is constructed in a structure in which a cathode and an anode are wound in a circle while a separator is interposed between the cathode and the anode. A cylindrical center pin is disposed at the center of the winding (the center of the jelly roll). The center pin is generally made of a metal material to exhibit predetermined strength. The center pin is constructed in a hollow cylindrical structure formed by rolling a metal sheet. The center pin serves to fix and support the electrode assembly. In addition, the center pin serves as a passage to discharge gas generated by internal reaction of the battery when charging, discharging, and operating the battery.
The material for the cylindrical container is not particularly restricted. Preferably, the cylindrical container is formed of stainless steel, steel, aluminum, or an equivalent thereof.
The cylindrical battery according to the present invention may be a lithium secondary battery having high energy density, high discharge voltage, and high output stability. The lithium secondary battery generally includes a cathode, an anode, a separator, and a nonaqueous electrolyte containing lithium salt.
The cathode may be manufactured, for example, by applying a mixture of a cathode active material, a conductive material, and a binder to a cathode current collector and drying the applied mixture. A filler may be further added as needed. The anode may be manufactured by applying an anode material to an anode current collector and drying the applied anode material. The above-mentioned ingredients may be further added as needed.
The separator is disposed between the anode and the cathode. The separator may be made of an insulative thin film exhibiting high ion permeability and high mechanical strength.
The nonaqueous electrolyte containing lithium salt consists of a nonaqueous electrolyte and lithium salt. The nonaqueous electrolyte may include a liquid nonaqueous electrolyte, a solid nonaqueous electrolyte, and an inorganic solid nonaqueous electrolyte.
The current collector, the electrode active material, the conductive material, the binder, the filler, the separator, the electrolyte, and the lithium salt are well known in the art to which the present invention pertains, and therefore, a detailed description thereof will not be given.
The lithium secondary battery according to the present invention may be manufactured by a general method well known in the art to which the present invention pertains. That is, the lithium secondary battery may be manufactured by placing a porous separator between a cathode and an anode and injecting an electrolyte thereinto.
For example, as previously described, the cathode may be manufactured by applying a slurry including a lithium transition metal oxide active material, as a cathode active material, a conductive material, and a binder to a current collector and drying and pressing the slurry. In the same manner, as previously described, the anode may be manufactured by applying slurry including a carbon active material, as an anode active material, a conductive material, and a binder to a thin current collector and drying the slurry.
The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
Now, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be noted, however, that the scope of the present invention is not limited by the illustrated embodiments.
Referring first to
The cap assembly 300 is constructed in a structure in which a top cap 310, a PTC element 350, and a safety vent 320 for reducing the internal pressure of the battery are disposed in an airtight gasket 400 mounted at an upper beaded part 210 of the cylindrical container 200 while being in tight contact with one another.
A current interruptive device 600 configured to rupture for interrupting current when the interior pressure of the battery increases is coupled to the lower end of the safety vent 320 by welding. The current interruptive device 600 is surrounded by a current interruptive device gasket 700.
The PTC element 350 is disposed between the top cap 310 and the safety vent 320 in a tight contact state. The PTC element 350 greatly increases battery resistance, when the internal temperature of the battery increases, to interrupt current. The top cap 310 protrudes upward at the middle thereof to serve as a cathode terminal for connection with an external circuit. A plurality of exhaust ports 312 are formed along the circumference of the protrusion of the top cap 310 such that pressurized gas is discharged out of the cylindrical container 200 through the exhaust ports 312.
The structure of the safety vent 320 of the cap assembly 300 constructed as described above will be described in more detail with reference to
The safety vent 320 is a thin-film structure transmitting current. At the center of the safety vent 320 is formed a depression 322, which is depressed downward. A first notch 324 is formed at an upper bent portion of the safety vent 320. Second notches 326 are formed at a lower bent portion of the safety vent 320.
As shown in
Also, the second notches 326 are formed at the lower bent portion of the safety vent 320. The second notches 326 are configured in the shape of open curves, opposite ends of which are open. Two non-notch portions 340 are located at the open opposite end regions of the second notches 326. The non-notch portions 340 prevent the second notches 326 from being separated by cutoff. In order to securely prevent the separation of the second notches 326, it is preferable for the non-notch portions 340 to be located at positions where the non-notch portions 340 are not aligned with the non-notch portion 330 of the first notch 324. More preferably, as shown in the drawing, the second notches 326 are located approximately at a right angle to the center line of the non-notch portion 330 of the first notch 324, and the two non-notch portions 340 are opposite to each other.
Referring to
On a concentric circle of the protrusion 620 are formed three through slits 630 and bridges 640 having notches 650 to interconnect the through slits 630.
Also, three through holes 610 for gas discharge are formed at the outer circumference of the current interruptive device 600 in the shape of an arc such that the through holes 610 are radially symmetrical about the central axes thereof. The sum of areas of the through holes is equivalent to 30% of the entire area of the current interruptive device 600. Consequently, the amount of high-pressure gas discharged from the battery is increased, thereby achieving a reliable current interruption effect. The through holes 610 are arranged at intervals of approximately 120 degrees. The shapes and sizes of the respective through holes 610 are the same. The distances between the respective through holes 610 are approximately the same. With this structure, it is possible for the current interruptive device 600 to maintain high mechanical strength while maximizing the amount of discharged gas.
It is preferable for a size of a circle (See the dotted line) linking the center lines of the respective through holes 610 to be approximately equal to the size of the first notch 324 of the safety vent 320 (See
Referring to
Referring to
Referring to
Referring to these drawings, when the internal pressure of the battery abnormally increases, pressurized gas passes through the through holes 610 and the through slits 630 of the current interruptive device 600 to apply upward pressure to the safety vent 320.
As a result, as shown in
When the internal pressure of the battery continuously increases in spite of the current interruption, with the result that the internal pressure of the battery reaches a second critical pressure level, as shown in
Hereinafter, examples of the present invention will be described in more detail. It should be noted, however, that the scope of the present invention is not limited by the illustrated examples.
As shown in
Also, as shown in
Also, as shown in
The outer circumference of the current interruptive device was inserted into the current interruptive device gasket, and the bottom of the depression of the safety vent was fixed to the top of the protrusion of the current interruptive device by laser welding.
A jelly roll type electrode assembly, which was constructed in a structure in which a porous separator made of polyethylene was disposed between a cathode made of lithium cobalt oxide and an anode made of graphite, was inserted into a cylindrical container, and a disc-shaped insulating member was mounted to the cylindrical container. After that, the top of the cylindrical container was beaded such that the disc-shaped insulating member was fixed to the cylindrical container. Subsequently, a gasket in which the safety vent, to which the current interruptive device was fixed, a PTC element, and a top cap were fitted were inserted into the beaded part. After that, the upper end of the cylindrical container was bent inward by pressing to clamp the gasket. In this way, a battery was manufactured.
A battery was manufactured in the same method as in Example 1 except that the thickness of the first notch was 0.1 mm, and the thickness of each of the second notches was 0.06 mm, when manufacturing the safety vent.
A battery was manufactured in the same method as in Example 1 except that the diameter of the first notch was 7 mm, and the thickness of the first notch was 0.06 mm, when manufacturing the safety vent.
A battery was manufactured in the same method as in Example 1 except that the sum of areas of the through holes of the current interruptive device was equal to approximately 18% of the entire area of the current interruptive device.
Nail tests were carried out on the batteries manufactured according to Examples 1 to 3 and Comparative example 1. Table 1 below reveals the results of the nail tests.
It can be seen from Table 1 above that, when the current interruptive device in which the area ratio of the through holes was 30% was used according to the present invention, the batteries did not explode, or the battery containers were not deformed. For the battery according to Comparative example 1 using the current interruptive device in which the area ratio of the through holes was 18%, on the other hand, the battery exploded during the nail test. Also, when the second notches were cut off, and therefore, the discharge of gas through the safety vent was not smoothly achieved, as in Examples 2 and 3, the batteries did not explode, but the battery containers were deformed.
For a high-capacity battery, it is not possible to sufficiently discharge gas when the size of the cutoff of the safety vent and the size of the through holes of the current interruptive device are not sufficiently large. When the cutoff of the safety vent corresponds to the second notches located inside, the inclined inside notch of the safety vent resists gas discharge after the notches are cut off, even though the diameter of the notches is increased.
As discussed above, it is possible to effectively discharge pressurized gas out of the battery by using the first notch as the cutoff of the safety vent as well as increasing the area of the through holes of the current interruptive device, thereby improving safety of the battery.
As apparent from the above description, the cap assembly according to the present invention includes the current interruptive device provided with the through holes having a relatively large area. As a result, it is possible to effectively discharge high-pressure gas out of the battery. Furthermore, when the notch, configured to rupture, of the safety vent is formed such that the notch corresponds to the through holes, it is possible to achieve the discharge of the high-pressure gas in a straight line. When high-pressure gas is generated, therefore, it is possible to achieve prompt cutoff of the safety vent and to achieve rapid discharge of the gas, thereby greatly improving safety of the battery.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2008-0100679 | Oct 2008 | KR | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/KR2009/005407 | Sep 2009 | US |
| Child | 12846873 | US |
