JP6047632B2 - Secondary battery - Google Patents

Secondary battery Download PDF

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JP6047632B2
JP6047632B2 JP2015127201A JP2015127201A JP6047632B2 JP 6047632 B2 JP6047632 B2 JP 6047632B2 JP 2015127201 A JP2015127201 A JP 2015127201A JP 2015127201 A JP2015127201 A JP 2015127201A JP 6047632 B2 JP6047632 B2 JP 6047632B2
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gas discharge
battery
gas
electrode group
secondary battery
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JP2015195219A (en
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拓郎 綱木
拓郎 綱木
正明 岩佐
正明 岩佐
佐々木 孝
孝 佐々木
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日立オートモティブシステムズ株式会社
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Description

  The present invention relates to a secondary battery.

  An electrode group is prepared by laminating a sheet-like positive electrode and negative electrode with a separator interposed therebetween, and this electrode group is placed in a metal or resin sealed container filled with an electrolytic solution and connected to both electrodes of the electrode group. A lithium ion secondary battery provided with a terminal is widely known.

  In the secondary battery, when the electrode group generates heat due to an abnormal operation, a large amount of gas is generated, and the internal pressure of the battery may increase. Abnormal operation includes overcharge, heating, internal short circuit due to external load, and the like.

  Conventionally, a gas discharge valve is provided in the battery container, and when the internal pressure of the container rises, gas is discharged from the gas discharge valve to prevent the battery container from bursting. However, when the gas is generated, the electrode group may move due to the internal pressure of the container and the gas discharge valve may be blocked.

  In Patent Document 1, in a secondary battery in which a gas discharge valve is provided on a side surface of a container, the electrode group, the side surface of the container, The cross-sectional area (first cross-sectional area) of the gap between the electrodes is made larger than the cross-sectional area (second cross-sectional area) of the gap between the electrode group and the container bottom surface.

JP 2007-220418 A

  In the secondary battery described in Patent Document 1, the gas discharge valve can be reliably cleaved so that the gas discharge valve is not blocked even when the electrode group moves. However, depending on the relative size of the opening area of the gas exhaust valve and the first and second cross-sectional areas, the internal pressure reducing effect in the battery container may not be sufficient due to the gas that continues to be generated after the gas exhaust valve is opened. .

The secondary battery according to the first aspect of the present invention has a wound electrode group having a curved portion and a flat portion, and has a container having an opening, and a lid that closes the opening and is provided with a gas discharge valve. The container has a pair of side surfaces facing the winding axis of the wound electrode body, and in the container, a first gap formed by the wound electrode group and the one side surface, A second gap formed by the curved portion and the lid is provided, and the area of the gas exhaust valve is larger than the minimum cross-sectional area of the gap formed by the first gap and the second gap. Is.
The secondary battery according to the second aspect of the present invention is such that the maximum gas discharge flow rate in the second gap portion is larger than the maximum gas discharge flow rate in the first gap portion.
In the secondary battery according to the third aspect of the present invention, the gas discharge valve is unevenly distributed on one side of the container.

  The battery of the present invention can suppress an increase in the pressure inside the battery outer container even after the gas discharge valve is opened.

1 is an external perspective view showing a first embodiment of a secondary battery according to the present invention. The disassembled perspective view of the secondary battery of FIG. The perspective view which shows the winding type electrode group in the secondary battery of FIG. The perspective view which shows the winding type electrode group of FIG. 3A which compressed the uncoated part previously, when connecting with a collector. The longitudinal cross-sectional view which shows the flow of the gas at the time of gas exhaust valve cleavage in the secondary battery of FIG. The cross-sectional view which follows the VV arrow line of FIG. The longitudinal cross-sectional view which follows the VI-VI arrow line of FIG. The longitudinal cross-sectional view which follows the VII-VII arrow line of FIG. The top view of FIG. The conceptual diagram which shows that the flow-path cross-sectional area of the gas flow path in 1st Embodiment is S1 <S2 <S3. The conceptual diagram which shows the comparative example which changed the flow-path cross-sectional area of the gas flow path with S1> S2> S3. The graph which shows the change of a battery internal pressure when a secondary battery is forced to short-circuit internally. The longitudinal cross-sectional view which shows the flow of the gas at the time of gas exhaust valve cleavage in 2nd Embodiment of the thin lithium ion secondary battery by this invention.

  An embodiment in which the present invention is applied to a lithium ion secondary battery for a hybrid vehicle will be described with reference to the drawings.

[First Embodiment]
As shown in FIGS. 1 and 2, the thin lithium ion secondary battery has a thin shape with a substantially rectangular parallelepiped appearance. This secondary battery has a bottomed metal battery can 1 and a flat metal battery cover 2 whose contour matches the opening of the battery can 1. The battery can 1 is made, for example, from an aluminum alloy material into a thin rectangular parallelepiped having a pair of wide surfaces 1W, a pair of elongated narrow surfaces 1N, and a bottom surface 1B.

  The battery cover 2 is made of an aluminum alloy in this example. The battery cover 2 is joined to the inner periphery of the opening 10 of the battery can 1 by laser (beam) welding, and the opening 10 of the battery can 1 is sealed. A battery outer container is constituted by the battery can 1 and the battery lid 2.

  At the center of the battery lid 2, there is provided a gas discharge valve 3 for cleaving at a preset pressure when the pressure in the battery outer casing rises and releasing the gas to the outside. The gas discharge valve 3 is a thin film member made of substantially the same metal material as the battery lid 2 and is joined to the battery lid 2 by laser welding or the like.

A bag-shaped insulating sheet 12 is accommodated in the internal space of the battery outer casing, and the wound electrode group 6 is accommodated in the insulating sheet 12. Thereby, the wound electrode group 6 is insulated from the battery outer casing. Further, an electrolytic solution or the like is stored in the battery outer case.
In addition, the secondary battery of this embodiment is neutral in which the battery can 1 and the battery lid 2 have no polarity.

  As shown in FIG. 3A, the wound electrode group 6 has a flat wound structure in which a strip-shaped separator 6C, a strip-shaped negative electrode plate 6E, a strip-shaped separator 6C, and a strip-shaped positive electrode plate 6D are sequentially stacked and wound. . A separator 6C is wound around the winding start end of the wound electrode group 6 several times, and positive and negative plates 6D and 6E are wound around the separator 6C with the separator 6C interposed therebetween. At the winding end end portion of the wound electrode group 6, the separator 6C is wound several times, and the outermost periphery (lowermost surface in FIG. 2) of the separator 6C is covered with an adhesive tape (not shown) to prevent unwinding. Stopped.

  The positive electrode plate 6D is produced by applying a positive electrode active material mixture on both surfaces of an aluminum alloy foil. For example, a positive electrode active material mixture containing a lithium-containing transition metal double oxide such as lithium manganate is applied (applied) substantially uniformly and substantially uniformly. At one end portion in the winding axis direction along the longitudinal direction (winding direction) of the aluminum alloy foil, a positive electrode uncoated portion 6A that is not coated with the positive electrode active material mixture is formed on both surfaces. That is, in the positive electrode uncoated portion 6A, the aluminum alloy foil (positive electrode current collector) is exposed.

  The negative electrode plate 6E is produced by applying a negative electrode active material mixture on both sides of a copper alloy foil. For example, a negative electrode active material mixture containing a carbon material such as graphite capable of inserting and extracting lithium ions is applied substantially uniformly and substantially uniformly. At the other end in the winding axis direction along the longitudinal direction (winding direction) of the copper alloy foil, negative electrode uncoated portions 6B in which the negative electrode active material mixture is not coated are formed on both surfaces. That is, in the negative electrode uncoated portion 6B, the copper alloy foil (negative electrode current collector) is exposed.

  Separator 6C is made of a microporous sheet material through which lithium ions can pass. In this example, a polyethylene sheet having a thickness of several tens of μm is used.

As shown in FIG. 2, through holes (not shown) for connecting the inside and outside of the battery are formed in the left and right ends of the battery lid 2, and a positive electrode conductive member 4 and a negative electrode conductive member 5 are formed in the through holes. Each is mounted via an insulating sealing material 7. The positive electrode conductive member 4 and the negative electrode conductive member 5 exposed to the outside of the battery lid 2 serve as positive and negative electrode external terminals 4T and 5T, respectively, and connect the wound electrode group 6 to an electric load or a charging power source outside the battery. The positive electrode conductive member 4 and the negative electrode conductive member 5 extending inside the battery can are a positive electrode current collector 4S and a negative electrode current collector 5S. The positive electrode current collector 4S is bonded to the positive electrode uncoated portion 6A at the flat positive electrode side bonding portion 4A, and the negative electrode current collector 5S is bonded to the negative electrode uncoated portion 6B at the flat negative electrode side bonding portion 5A. Has been.
The wound electrode group 6 is integrated with the battery lid 2 by the positive and negative electrode conductive members 4 and 5 and is supported by the battery lid 2 in a cantilever state.

  FIG. 3B is a perspective view of the electrode group 6 in which the central regions of the uncoated portions 6A and 6B are compressed. The electrode group 6 has a flat portion 6P formed at the center, and a compressed laminated body compressed flat portion 6S formed at the center region of both ends. A curved portion 6W accompanying winding is formed above and below the flat surface portion 6P of the electrode group 6. The curved portion 6W is formed by bending the positive and negative electrode foils during winding, and the positive and negative electrode foils are laminated, but is not compressed. In FIG. 3B, the four corners of the curved portion 6W are referred to as a laminate curved end portion 6E.

  3B, in the battery can 1, the front and back plane portions 6P are opposed to the pair of wide surfaces 1W of the battery can 1 with a predetermined gap, and the four curved end portions 6E are the left and right sides of the battery can 1. It faces the narrow surface 1N with a predetermined gap. Further, the upper surface of the curved portion 6W is disposed to face the inner surface of the battery lid 2 with a predetermined gap, and the lower surface of the curved portion 6W is disposed to face the bottom surface 1B of the battery can 1 with a predetermined gap. These four gaps are locations that can be flow paths for the gas generated inside the electrode group 6. The gas flow path will be described later.

  The region where the wound electrode group 6 is joined to the positive and negative electrode current collectors 4S and 5S at the uncoated portions 6A and 6B is the above-described laminate compression plane portion 6S. The laminate compression plane portion 6S of the positive and negative electrode foils wound a plurality of times is ultrasonically bonded to the positive and negative electrode current collectors 4S and 5S, and the gap between the positive and negative electrode foils is also bonded. Therefore, the gas generated by short circuit, heat generation, or the like inside the wound electrode group 6 is hardly discharged out of the electrode group from the laminate compression flat portion 6S.

  On the other hand, since the curved portion 6W of the electrode group 6 is not compressed, minute gaps are formed between the positive and negative foils constituting the laminated body at the four end portions 6E of the curved portion 6W. These minute gaps can serve as a discharge channel for gas generated inside the electrode group. Therefore, the laminated body curved end portions 6E at the four corners of the electrode group 6 function as gas discharge portions.

  When gas is generated due to heat generation due to a short circuit or the like inside the wound electrode group 6, the internal pressure of the battery outer casing rises and the gas discharge valve 3 is opened. As a result, the battery outer container is prevented from rupturing, and the generated gas is discharged from the gas discharge valve 3 through the following gas discharge passage.

The gas discharge flow path until the gas generated in the battery can 1 is discharged from the gas discharge valve 3 will be described.
The curved portion end 6E has a minute gap through which gas flows between a plurality of laminated foils. The broken line arrow A1 indicates the flow of the minute gap in the positive electrode side curved end 6E, and the broken line arrow A2 indicates the flow of the minute gap in the negative electrode side gas discharge part 6E. That is, as shown by broken line arrows A1 and A2 in FIG. 4, the gas generated inside the wound electrode group 6 flows in the direction of the wound axis of the wound electrode group 6 in the curved portion end 6E.

The gas discharged from the curved end portion 6E of the electrode group 6 is a vertical flow path formed by the four curved end portions 6E of the electrode group 6 facing the left and right narrow surfaces 1N of the battery can 1 with a predetermined gap. Flows into the battery lid 2 as the gases B1 and B2. This vertical flow path is referred to as a first gas discharge flow path FL1.
The gas flowing through the first gas discharge flow path FL1 reaches the gas discharge valve 3 via a horizontal flow path formed so that the upper surface of the curved portion 6W faces the inner surface of the battery lid 2 with a predetermined gap. This horizontal flow path is referred to as a second gas discharge flow path FL2.

  The gases A1 and A2 inside the electrode group 6 reach a space between both end faces of the electrode group 6 and the battery can narrow surface 1N, and vertically pass through the first gas discharge channel FL1 toward the battery lid 2. Flowing. Further, this gas flow flows into the horizontal flow path that is the second gas discharge flow path FL <b> 2 between the curved portion 6 </ b> W of the electrode group 6 and the battery cover 2, and flows toward the gas discharge valve 3. In FIG. 4, the vertical gas toward the battery lid 2 on the positive electrode side and the negative electrode side is indicated by broken line arrows B1 and B2. Moreover, the horizontal gas which goes to the gas exhaust valve 3 in the positive electrode side and the negative electrode side is shown with broken-line arrows C1 and C2. The horizontal gas indicated by the arrows C1 and C2 toward the gas discharge valve 3 is finally discharged from the cleavage opening of the gas discharge valve 3 to the outside as indicated by the arrow D.

As shown in FIGS. 4 and 5, the cross-sectional area of the first gas discharge flow path FL1 formed in the space between the both end faces of the electrode group 6 and the narrow surface 1N of the battery can is represented by S1A and S1B. S1
S1 = S1A + S1B Formula (1)
It is expressed.

  6 is a cross-sectional view of the main part shown by cutting along the VI-VI cutting line of FIG. 4, and FIG. 7 is a cross-sectional view of the main part shown by cutting along the VIVIII cutting line of FIG. Among the gas discharge passages from the curved end 6E of the electrode group 6 to the gas discharge valve 3, the positive and negative electrode conductive members 4 and 5 are connected to the second gas discharge passage FL2 through which the horizontal gases C1 and C2 flow. The sealant 7 extends perpendicularly and protrudes, and is a narrow space containing many obstacles. Therefore, the minimum flow path cross-sectional area of the second gas discharge flow path FL2 is the effective cross-sectional area of the horizontal flow path. Here, the effective cross-sectional area is a value obtained by excluding the area of the obstacle protruding into the horizontal flow path from the cross-sectional area of the flow path partitioned by the curved portion 6W of the electrode group 6 and the battery lid 2. The area of the obstacle is an area of the obstacle perpendicular to the flow path.

As shown in FIG. 6 and FIG. 7, when the minimum flow path cross-sectional areas of the second gas discharge flow paths FL2 through which the horizontal gas flows shown by broken line arrows C1 and C2 in FIG. 4 flow are S2A and S2B, respectively,
S2 = S2A + S2B Formula (2)
It is expressed.

  As shown in FIG. 8, the opening area of the gas discharge valve 3 provided in the center of the battery lid 2 is S3, which is the maximum area of the cleavage opening. The cleavage opening does not necessarily open to the opening area S3, but usually has an opening area S3 or a value close thereto.

In the secondary battery according to the embodiment of the present invention, the flow path cross-sectional areas S1, S2, and S3 are S1 <S2 <
It is set to be S3, and the cross-sectional area of the flow path is sequentially enlarged toward the downstream.

  When the wound electrode group 6 generates heat, gas is generated and the pressure inside the battery outer container rises. When the gas pressure becomes equal to or higher than the cleavage pressure of the gas discharge valve 3, the gas discharge valve 3 is opened. As a result, the pressure inside the battery outer casing once drops. Even after the gas discharge valve 3 is cleaved, gas continues to be generated from the electrode group 6. This gas flows as the gas indicated by the broken arrows A1, A2, B1, B2, C1, C2, D from the first gas discharge flow path FL1 through the second gas discharge flow path FL2, and the gas discharge valve 3 is cleaved. It is discharged out of the battery can 1 through the opening.

  As shown in FIG. 9, in the secondary battery of the present embodiment, the gas discharge capacity of the second gas discharge channel FL2 through which the gas indicated by the broken arrows C1 and C2 flows when the gas is discharged after the gas discharge valve 3 is cleaved is The gas discharge capacity of the first gas discharge flow path FL1 through which the gas indicated by the broken arrows B1 and B2 flows is higher. Moreover, the gas discharge capability by the opening which the gas discharge valve 3 was cleaved is higher than the 2nd gas discharge flow path FL2 into which the gas shown with broken-line arrow C1, C2 flows. Therefore, when the gas flow indicated by the broken line arrows C1 and C2 goes from the gas discharge valve 3 to the outside as indicated by the broken line arrow D, it is possible to suppress an increase in pressure in the second gas discharge flow path FL2. As a result, an increase in pressure inside the battery outer container is suppressed, and accidents such as rupture of the battery outer container are prevented.

  As in the comparative example shown in FIG. 10, assuming that the flow path cross-sectional areas S1, S2, and S3 are set to satisfy S1> S2> S3, the second gas discharge through which the gas indicated by the dashed arrows C1 and C2 flows. The gas discharge capacity of the flow path FL2 is lower than the gas discharge capacity of the first gas discharge flow path FL1 through which the gas indicated by the broken arrows B1 and B2 flows. Furthermore, the gas discharge capability due to the opening of the gas discharge valve 3 indicated by the broken arrow D is lower than the gas discharge capability of the second gas discharge flow path FL2.

When the gas discharge capacity of a plurality of flow paths from the electrode group (gas generation source) 6 to the gas discharge valve 3 is set as in the comparative example, the battery can internal pressure cannot be effectively reduced as follows. .
For example, the maximum gas discharge flow rate in the first gas discharge flow path FL1 of gas indicated by broken line arrows B1 and B2 is 10 L / S, and the amount of generated gas, that is, the flow rate of gas indicated by broken line arrows A1 and A2 is 10 L / S. , The maximum gas discharge flow rate in the second gas discharge channel FL2 is less than 10 L / S, so the pressure in the first gas discharge channel FL1 increases.
Similarly, since the maximum gas discharge amount of the gas discharge valve 3 is smaller than the maximum gas discharge amount in the second gas discharge flow path FL2 indicated by the dashed arrows C1 and C2, the pressure in the second gas discharge flow path FL2 increases. To do.

  Therefore, there is a possibility that the internal pressure of the battery outer casing does not decrease despite the gas discharge valve 3 being cleaved, due to the gas generated at the time of occurrence of an abnormality, and the pressure inside the battery outer casing is increased.

  On the other hand, in the secondary battery according to the present embodiment, the cross-sectional areas of the gas flow paths are S1 <S2 <S3, and the cross-sectional areas of the gas flow paths are sequentially increased toward the downstream. As a result, the gas discharge capacity increases toward the downstream, the gas is discharged very smoothly, and the pressure inside the battery outer container does not increase after the gas discharge valve 3 is opened.

[Forced internal short circuit test]
A lithium ion battery with a changed gas discharge passage area was manufactured, and a forced internal short circuit test was performed assuming an abnormal operation, and the effect of the present invention was confirmed.

  In the forced internal short-circuit test, a thin lithium ion secondary battery having a channel cross-sectional area of S1 <S2 <S3 is manufactured as sample 1 (embodiment), and the channel cross-sectional areas are S1 <S2 and S3 <S2. A thin lithium ion secondary battery was produced as Sample 2. A nail with a diameter of 5 mm and a tip angle of 60 ° was passed through the center of the wide surface of the battery to cause a short circuit, and then the internal pressure was measured until the gas generation event was completed. In addition, the battery capacity of the electrode group 6 used by the samples 1 and 2 is substantially equal.

As shown in FIG. 11, in the thin lithium ion secondary battery of Sample 2, the internal pressure increased due to a large amount of gas generated by the forced internal short circuit, and the gas discharge valve 3 was cleaved at a preset cleavage pressure. However, since the gas was not discharged smoothly thereafter, the pressure inside the battery outer container rose to a pressure slightly exceeding the cleavage pressure of the gas discharge valve 3.
In general, thin lithium ion secondary batteries are safe against pressures near the cleavage pressure, but when exposed to repeated overheating, repeated stress, etc. for a long period of time, the pressure increase near the cleavage pressure increases the durability of the battery outer container. There is a risk that the sex will decline.

  On the other hand, in the thin lithium ion secondary battery of Sample 1, the pressure increased due to a large amount of gas generated by the forced internal short circuit, the gas discharge valve 3 was opened at the cleavage pressure, and the gas was discharged smoothly thereafter. The pressure increase was suppressed.

  In addition, although the cleavage pressure of the gas exhaust valve 3 of the sample 1 and the sample 2 is different, this is a variation of a product.

[Second Embodiment]
A second embodiment of a thin lithium ion secondary battery according to the present invention will be described with reference to FIG. In the figure, the same or corresponding parts as those in the first embodiment are denoted by the same reference numerals, and description thereof is omitted. In the second embodiment, the position of the gas discharge valve in the first embodiment is deviated from the center of the battery lid.

  As shown in FIG. 12, in the thin lithium ion secondary battery, the gas discharge valve 3 is biased from the center of the battery lid 2. For this reason, in the gas flow path along the battery lid 2, the length of the flow path of the broken line arrow C1 and the flow path of the broken line arrow C2 are different. However, in the size of a practical thin lithium ion secondary battery for a hybrid vehicle, the influence of the deviation of the gas discharge valve 3 on the battery lid 2 on the gas discharge performance is in a negligible range. That is, the second embodiment has the same effect as the first embodiment.

[Modification]
The above description is one embodiment, and the present invention can be applied to secondary batteries having various structures that do not depart from the spirit of the present invention. The main feature of the present invention is that the cross-sectional area of the gas discharge passage until the gas generated inside the electrode group 6 is discharged from the gas discharge valve 3 is set larger toward the downstream. Therefore, the secondary battery having this main feature can be implemented with the following modifications, for example.

(1) At the winding start end of the electrode group 6, the separator 6 </ b> C was wound a plurality of times to substitute for the axis of the electrode group 6. However, the present invention can also be applied to an electrode group in which a separator, a negative electrode plate, a separator, and a positive electrode plate are wound on the outer peripheral surface of the shaft core.

(2) In the above embodiment, one end of the positive and negative electrode conductive members 4 and 5 is joined to the uncoated portions 6A and 6B of the electrode group 6, and the conductive member 4 protruding outside the container through the battery lid 2 The other end of 5 was used as external terminals 4T and 5T. However, the secondary battery according to the present invention is not limited to the shape and configuration of such a conductive member.

(3) In the above embodiment, the battery lid 2 covers the elongated rectangular opening facing the battery can bottom 1B, and the gas discharge valve 3 is provided on the battery lid 2. However, the present invention can also be applied to a secondary battery in which the wide surface 1W of the battery can 1 is sealed with the battery cover 2 and the gas discharge valve 3 is provided on the battery cover 2.

(4) In the embodiment, it has been described that the cross-sectional area of the first gas discharge flow path FL1 is larger than the cross-sectional area of the second gas discharge flow path FL2. However, the present invention includes the case where the cross-sectional area of the first gas discharge flow path FL1 and the cross-sectional area of the second gas discharge flow path FL2 are substantially equal. Therefore, in the present invention, the gas generated in the electrode group is discharged from the gas discharge valve, and the opening area when the gas discharge valve is opened is set to be larger than the cross-sectional area of the gas discharge flow path from the electrode group to the gas discharge valve. Can be applied to any secondary battery.

(5) The present invention can be applied to various secondary batteries having a wound electrode group, such as nickel hydride secondary batteries, in addition to lithium ion secondary batteries. The present invention can also be applied to various lithium ion capacitors having a wound electrode group.

Claims (2)

  1. A wound electrode group having a curved portion and a flat portion, and a container having an opening;
    In a secondary battery having a lid that closes the opening and is provided with a gas discharge valve,
    The container has a pair of side surfaces facing the winding axis of the wound electrode body,
    In the container, a first gap formed by the wound electrode group and one side surface, and a second gap formed by the curved portion and the lid are provided,
    The area of the gas discharge valve is larger than the minimum cross-sectional area of the gap formed by the second gap,
    The secondary battery , wherein a minimum cross-sectional area of the gap formed by the second gap is larger than a minimum cross-sectional area of the gap formed by the first gap .
  2. The secondary battery according to claim 1 ,
    The secondary battery according to claim 1, wherein the gas discharge valve is unevenly distributed on one side of the container.
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