JP2008159316A - Lithium ion occlusion/release type organic electrolyte storage battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase productivity by smoothly quickly conducting pre-occlusion of lithium ions into a negative electrode and decreasing frequencies handling lithium metal in a production process in a lithium ion occulusion/release type organic electrolyte storage battery having an electrode body formed by laminating a positive electrode made of a substance capable of reversely carrying lithium ions or anions and a negative electrode capable of occluding/releasing lithium ions which are an electrolyte cation through a separator in order. <P>SOLUTION: In the storage battery, a through hole 52 passing through a laminated electrode body 20 in the laminated direction, a lithium metal 41 for pre-occluding lithium ions into a negative electrode is filled in the through hole 52, the lithium metal 41 is electrically connected to a conductor 25 arranged on the outermost layer of the laminated electrode body 20, and the lithium metal 41 is electrically connected to the negative electrode on the inside or the outside of the storage battery through the conductor 25. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a lithium ion storage / release type organic electrolyte storage battery, and more particularly, a separator is interposed between a positive electrode capable of storing / releasing electrolyte anions and a negative electrode capable of storing / releasing lithium ions as electrolyte cations. However, the present invention relates to one using an electrode body having a laminated structure which is sequentially laminated.

  In recent years, power storage means capable of rapid charging / discharging of relatively large electrical energy have been required for load leveling in wind power generation, solar cells, etc., countermeasures for instantaneous voltage drop / power failure, energy recovery in automobiles, etc. I came.

  Conventionally, lithium ion secondary batteries that have high energy density and can be charged have been provided as power storage means. However, the lithium ion secondary battery is rapidly deteriorated in characteristics due to repeated charge and discharge, and has a limited number of charge / discharge cycles (lifetime). In addition, the time required for charging is long, and rapid charging as required by the energy regeneration is impossible. That is, there was a problem in charge / discharge characteristics. This is a problem common to all secondary batteries as well as lithium ion secondary batteries.

  If attention is paid only to the charge / discharge characteristics, the electric double layer capacitor is more suitable than the secondary battery. The charge / discharge characteristics of the electric double layer capacitor are superior to those of the secondary battery, and can be used without maintenance for a long period of time, and can be rapidly charged / discharged. However, the electric double layer capacitor can have a very large capacity (capacitance) as a capacitor, but the chargeable / dischargeable capacity is considerably inferior to that of the lithium ion secondary battery.

  In view of this, a lithium ion storage / release type organic electrolyte storage battery has been proposed that has the characteristics of combining an electric double layer capacitor and a lithium ion secondary battery. This storage battery is configured using a positive electrode capable of inserting and extracting anions, a negative electrode capable of inserting and extracting lithium ions, and an electrolyte containing a lithium salt (see Patent Documents 1 and 2).

  In the above lithium ion secondary battery, a composite oxide containing lithium (for example, lithium cobaltate) is used for the positive electrode, and a reversible process of charge and discharge is performed by exchanging lithium ions between the positive electrode and the negative electrode through an electrolytic solution. Is called. On the other hand, in the lithium ion storage / release type organic electrolyte storage battery, a reversible process of charge / discharge is performed by storage / release of electrolyte anions at the positive electrode and storage / release of lithium ions (electrolyte cations) at the negative electrode. .

  This lithium ion storage / release type organic electrolyte storage battery has such properties that the lithium ion secondary battery and the electric double layer capacitor have the respective advantages. That is, the charge / discharge cycle characteristics are superior to each stage as compared with the lithium ion secondary battery, and the charge / discharge capacity (capacity capable of being charged / discharged) is greater than each stage of the electric double layer capacitor.

  This lithium ion storage / release type organic electrolyte storage battery can be suitably used as a high-performance capacitor-type secondary battery. It can also be suitably used as a power storage means for performing load leveling, instantaneous voltage drop / power failure countermeasures, energy regeneration in automobiles and the like.

  The lithium ion storage / release type organic electrolyte storage battery is the same as a conventional lithium ion secondary battery in that an electrolyte containing lithium ions is used. Unlike lithium ion secondary batteries, lithium ion is stored in the positive electrode. Charging / discharging is performed by using anions and lithium ions (cations) present as electrolyte components in the electrolyte without using a substance to be supplied (for example, lithium cobaltate).

  The positive electrode occludes anions in the electrolyte during charging and releases them during discharging. The negative electrode occludes lithium ions in the electrolyte during charging and releases it during discharging. A reversible charging / discharging process is performed by reversible occlusion / release of these anions and lithium ions.

  Here, in order for the reversible process of charge / discharge to be efficiently performed without causing a gas generation reaction of the electrolytic solution, the negative electrode covers the entire range from the initial charge stage (or the final discharge stage) to the final charge stage (or the initial discharge stage). Must be stably fixed around the lithium potential. Therefore, the negative electrode is preliminarily occluded (doped) with lithium ions, so-called pre-occlusion (pre-doping). This pre-occlusion can be performed by arranging lithium metal in the electrolyte and electrically connecting the lithium metal to the negative electrode.

  Various structures of the lithium ion storage / release type organic electrolyte storage battery have been proposed. In order to ensure a large facing area between the positive electrode and the negative electrode, the positive electrode and the negative electrode are sequentially stacked with a separator in between. A laminated structure has been proposed.

For this reason, a positive electrode and a negative electrode are each formed in a sheet form. The sheet-like positive electrode is produced by attaching a positive electrode capable of occluding and releasing electrolyte anions to a current collector such as a metal foil by a method such as coating. Similarly, a sheet-like negative electrode is produced by attaching a negative electrode capable of inserting and extracting lithium ions, which are electrolyte cations, to a current collector such as a metal foil by a method such as coating. When producing the negative electrode, it was provided in a blank portion where the negative electrode was not attached to the current collector, and a lithium metal foil for pre-occlusion was adhered thereto (see Patent Documents 1 and 2).
JP 2000-21392 JP-A-9-147835

  The present inventors have revealed that the above-described conventional lithium ion storage / release type organic electrolyte storage battery has the following problems.

  (1) Lithium metal for preocclusion has been installed by sticking in advance to the current collector of the negative electrode sheet before constituting the electrode body, but this significantly impedes productivity. Lithium metal is highly reactive and requires special care when handling it. In particular, lithium metal in the state of being thinly developed in a foil shape is likely to react and is likely to ignite during the process. For this reason, the process after the installation of lithium metal requires special protective measures and reduces productivity. Therefore, when lithium metal is attached to the negative electrode current collector in advance, in addition to the increase in man-hours for the attachment, a series of processes including assembly of the subsequent electrode bodies are greatly complicated, and productivity is increased. It will be disturbed.

  (2) It took a long time for the lithium metal to dissolve in the electrolyte and be occluded by the entire negative electrode as lithium ions. This is considered because the lithium metal stuck on the current collector is confined between the layers of the electrode body. It has been found that the lithium metal placed in this state does not necessarily smoothly elute and move into the electrolyte, takes time to occlude in the negative electrode, and is difficult to uniformly occlude.

  The present invention has been made in view of the above problems, and the object thereof is a rectangular sheet in which a positive electrode capable of reversibly carrying lithium ions or anions is formed on a sheet-like positive electrode current collector. Electrode in which a sheet-like negative electrode part and a rectangular sheet-like negative electrode part on which a negative electrode capable of occluding and releasing lithium ions is formed on a sheet-like negative electrode current collector are alternately laminated with a separator interposed therebetween A lithium ion storage / release type organic electrolyte storage battery including a positive electrode current collector and an external terminal connected to each of the positive electrode current collector and the negative electrode current collector. In addition, it is possible to increase the productivity by making it possible to perform the process quickly and reducing the frequency of handling lithium metal in the production process.

  In addition, the present invention is a lithium battery that can reliably suppress gas generation due to decomposition of the electrolyte due to excessively high potential of the positive electrode during charging or charging / discharging in series connection. The object is to provide an ion storage / release type organic electrolyte storage battery.

  Other objects and configurations of the present invention will become apparent from the description of the present specification and the accompanying drawings.

The solution provided by the present invention is as follows.
(1) A rectangular sheet-like positive electrode part in which a positive electrode capable of reversibly carrying lithium ions or anions is formed on a sheet-like positive electrode current collector, and a negative electrode capable of occluding and releasing lithium ions are in a sheet form A rectangular sheet-shaped negative electrode portion formed on the negative electrode current collector is connected to each of the stacked electrode body alternately stacked with a separator interposed therebetween, and the positive electrode current collector and the negative electrode current collector. A lithium ion storage / release type organic electrolyte storage battery having an external terminal,
A through hole extending in the stacking direction is formed in the laminated electrode body, and lithium metal for preliminarily occluding lithium ions in the negative electrode is loaded into the through hole, and the lithium metal is placed in the outermost layer of the laminated electrode body. Lithium ion storage / release organic electrolyte storage battery characterized in that the lithium metal is conductively connected to a negative electrode on the inside or outside of the storage battery through conductive connection to the disposed conductor. .

(2) The means (1) includes a third electrode terminal as an external terminal separately from the positive electrode terminal and the negative electrode terminal, and the third electrode terminal is connected to the conductor.・ Releasable organic electrolyte storage battery.
(3) A lithium ion occlusion / release type organic electrolyte storage battery characterized in that in the means (2), a constant voltage circuit is provided so that the voltage between the third electrode terminal and the positive electrode terminal is a predetermined value or less.
(4) In any one of the means (1) to (3), a lithium ion occlusion / release is characterized in that a liquid-permeable insulating layer is interposed between the inner wall surface of the through hole and the lithium metal. Type organic electrolyte storage battery.

  A rectangular sheet-like positive electrode portion in which a positive electrode capable of reversibly carrying lithium ions or anions is formed on a sheet-like positive electrode current collector, and a negative electrode electrode capable of occluding and releasing lithium ions are provided for the sheet-like negative electrode collector. A rectangular sheet-shaped negative electrode portion formed on the electric current body is alternately laminated with a separator interposed therebetween, and an external body connected to the positive electrode current collector and the negative electrode current collector, respectively. This is a lithium ion storage / release type organic electrolyte storage battery equipped with a terminal, which makes it possible to smoothly and quickly perform the preliminary storage of lithium ions into the negative electrode, and the frequency of handling lithium metal in the production process. It can be reduced to increase productivity.

  Further, it is possible to reliably suppress gas generation due to decomposition of the electrolytic solution due to the potential of the positive electrode becoming too high during charging or charging / discharging in series connection.

  Operations / effects other than those described above will be apparent from the description of the present specification and the accompanying drawings.

  FIG. 1 shows a first embodiment of a lithium ion storage / release type organic electrolyte storage battery according to the present invention. In the figure, (a) is a cross-sectional view of the laminated electrode body 20 constituting the main part of the element, and (b) is an enlarged cross-sectional view of a part thereof. (C) is a top view showing a state in which the laminated electrode body 20 is housed in the element container 11 together with the electrolytic solution. A nonaqueous electrolytic solution using an organic medium is used as the electrolytic solution.

  In the lithium ion storage / release type organic electrolyte storage battery shown in the figure, a positive electrode portion 21 and a negative electrode portion 23 are sequentially stacked with a separator 22 interposed therebetween to form a rectangular flat stacked electrode body 20. In the positive electrode part 21, a positive electrode 211 made of a carbon material capable of reversibly supporting lithium ions or anions is attached in layers to both surfaces of a sheet-like current collector 212 made of a metal foil (Al) by coating or the like. The whole is formed in a sheet shape.

  Similarly, the negative electrode portion 23 has a negative electrode 231 capable of occluding and releasing lithium ions attached to both surfaces of a sheet-like current collector 232 made of metal foil (Cu) in a layered manner by coating or the like, so that the whole is a sheet. It is formed in a shape. The positive electrode portion 21 and the negative electrode portion 23 are sequentially stacked while sandwiching the separator 22 to form a rectangular flat stacked electrode body 20.

  The positive electrode part 21 occludes anions in the electrolyte during charging and releases them during discharging. The negative electrode part 23 occludes lithium ions (cations) in the electrolytic solution during charging and releases it during discharging. As a material for the positive electrode 211 and the negative electrode 231, a carbon material, particularly graphite, is suitable.

  The shape of the current collectors 212 and 232 is not particularly limited as long as they are good conductors that are inert to the electrolytic solution. For example, a metal net can be used, but the volumetric efficiency and current collection efficiency of the laminated electrode body 20 can be used. In view of the above, it is preferable to use a metal foil. As for the material, aluminum (Al) may be used for the positive electrode current collector 212 and copper (Cu) may be used for the negative electrode current collector 232.

  In order to connect the current collectors 212 and 232 to external terminals, conductive lead portions 213 and 233 to which no electrode material is applied are provided so as to protrude from the side of the laminated electrode body 20. The conductive lead portions 213 of the positive electrode current collector 212 are commonly connected to each other and welded to the positive electrode terminal 31. Similarly, the conductive lead portions 233 of the negative electrode current collector 232 are commonly connected to each other and welded to the negative electrode terminal 33. The positive electrode terminal 31 and the negative electrode terminal 33 are installed across the inside and outside of the element container 11 while keeping the sealed state of the element container 11.

  The element container 11 is not particularly limited as long as it can stably and hermetically contain the components of the storage battery including the electrolytic solution, but in this embodiment, a rectangular bag shape is formed by fusing an airtight flexible packaging material such as a laminate film. The soft container processed into is used. The laminated electrode body 20 is packaged and sealed in a vacuum packed state in the soft container together with the electrolytic solution.

  In addition to the above configuration, in the lithium ion storage / release type organic electrolyte storage battery of this embodiment, a through hole 52 is formed in the stacking direction of the stacked electrode body 20, and a lithium metal 41 for preliminary storage is inserted into the through hole 52.・ It is loaded. At the same time, a conductor 25 using a metal foil is disposed on the outermost layer of the laminated electrode body 20, and one end portion of the lithium metal 41 is attached to the conductor 25 for conductive connection. The conductor 25 is connected to a third electrode terminal 35 that is an external lead terminal different from the positive electrode terminal 31 and the negative electrode terminal 33.

  As with the positive electrode terminal 31 and the negative electrode terminal 33, the third electrode terminal 35 is installed across the inside and outside of the element container 11 while maintaining the sealed state of the element container 11. The third electrode terminal 35 is installed on the same side as the negative electrode terminal 33 and is electrically connected to the negative electrode terminal 33 by a jumper conductor 61.

  By connecting the third electrode terminal 35 and the negative electrode terminal 33, the lithium metal 41 is dissolved as lithium ions in the electrolytic solution, and moves to the negative electrode portion 23 to be occluded. At this time, in the lithium ion storage / release type organic electrolyte storage battery of this embodiment, the lithium metal 41 is loaded in the through hole 52 formed in the stacking direction of the electrode body 20 and appears on the inner wall surface of the through hole 52. From the laminated cross section, it moves to the negative electrode part 23 of each layer simultaneously and occluded. Further, the lithium ions diffuse radially from the through-hole 52 of the laminated electrode body 20 in the layer surface direction, so that the lithium ions move and are occluded in the entire negative electrode portion 23 of each layer by the shortest distance.

  Thereby, lithium ions can be preoccluded quickly and uniformly in the negative electrode portion 23 of each layer in the laminated electrode body 20. Therefore, the pre-occlusion which conventionally required a long time can be performed smoothly and uniformly in a significantly shorter time.

  The lithium metal 41 is inserted and loaded into the through hole 52 of the laminated electrode body 20, and this loading can be performed after the production process of the laminated electrode body 20. Therefore, at least in the production process until the laminated electrode body 20 is completed, it is not necessary to handle highly reactive lithium metal, thereby reducing the frequency of handling lithium metal in the production process and increasing productivity. Can do.

FIG. 2 shows a configuration of each layer of the laminated electrode body 20 having the through hole 52.
When the through-hole 52 is formed in the laminated electrode body 20, as shown in the figure, holes 521 that overlap each other are formed in the positive electrode portion 21, the separator 22, and the negative electrode portion 23 that form each layer of the laminated electrode body 20. Prepare in advance. When these are sequentially laminated to produce the laminated electrode body 20, the respective holes 521 overlap in the layer direction and form a through hole 52 perpendicular to the laminated surface of the laminated electrode body 20. The insertion and loading of the lithium metal 41 into the through hole 52 can be easily performed after the laminated electrode body 20 is completed.

  FIG. 3 shows a cross-sectional view of the main part of the second embodiment of the present invention. In this embodiment, the positive electrode portion 21 of the laminated electrode body 20 is configured to recede from the inner wall surface of the through hole 52. Thereby, it is possible to reliably avoid the lithium metal 41 loaded in the through hole 52 from coming into contact with the positive electrode portion 21. Since the electrolytic solution accumulates at the location where the positive electrode portion 21 is retracted, it is effective in preventing shortage of the electrolytic solution due to the loss of the electrolytic solution. Electrolyte depletion can occur over long periods of use.

  FIG. 4 shows a cross-sectional view of an essential part of a third embodiment of the present invention. In this embodiment, a liquid-permeable insulating layer 71 is interposed between the inner wall surface of the through hole 52 and the lithium metal 41. As a material of the insulating layer 71, for example, a porous resin or a nonwoven fabric is preferable. Further, the same material as the separator 22 may be used.

  In this embodiment, it is possible to reliably prevent the lithium metal 41 loaded in the through-hole 52 from coming into contact with the positive electrode portion 21, and the electrolyte solution is retained in the insulating layer 71, whereby the lithium metal 41 As a result, the lithium ions are smoothly moved and the lithium ions are moved, so that the lithium ions can be occluded into the negative electrode portion 23 more smoothly and quickly.

  FIG. 5 shows a cross-sectional view of an essential part of the fourth embodiment of the present invention. In this embodiment, the conductor 25 is disposed on one end side of the lithium metal 41 loaded in the through hole 52, and the liquid-permeable insulator 72 is placed on the other end side.

  This embodiment is particularly effective when a soft container made of an airtight flexible packaging material is used as the element container 11 (see FIG. 1). That is, the laminated electrode body 20 is housed and compressed in a soft container in a vacuum packed state, so that the laminated shape can be stably held. At this time, the lithium metal 41 loaded in the through hole 52 is The insulator 72 and the conductor 25 are sandwiched from both ends and positioned stably, and the connection stability with the conductor 25 is also improved. In order to reliably obtain this effect, it is desirable to install the insulator 72 so that it protrudes slightly from the outermost layer of the electrode body 20, as shown in FIG.

  FIG. 6 shows a cross-sectional view of a relevant part of a fifth embodiment of the present invention. In the same figure, (a) is a principal part sectional view showing a laminated electrode body 20 constituting the main part of the element, and (b) is a top view showing a state in which the laminated electrode body 20 is housed in an element container 11 together with an electrolytic solution. It is.

  In this embodiment, through holes 52 are formed at a plurality of locations (two locations) of the laminated electrode body 20, and lithium metal 41 is loaded into each through hole 52. Thereby, lithium ions eluted from the lithium metal 41 move radially from the plurality of locations inside the laminated electrode body 20 in the layer surface direction of the laminated electrode body 20 and are occluded in the negative electrode portion 23 of each layer. . For this reason, occlusion of lithium ions into the negative electrode portion 23 can be performed more quickly and smoothly.

  In addition, it is preferable to use the structure of the said embodiment together, such as interposing the insulating layer 71 which retains electrolyte solution between the lithium metal 41 and the inner wall face of the through-hole 52.

  The lithium ion storage / release type organic electrolyte storage battery of the present invention described above has, as an external terminal, the third electrode terminal 35 that is conductively connected to the lithium metal 41 in addition to the positive electrode terminal 31 and the negative electrode terminal 33. By using the third electrode terminal 35, it is possible to shorten the pre-occlusion time of lithium ions and to suppress the generation of gas during use of the lithium ion storage / release type organic electrolyte storage battery. .

  That is, as shown in FIG. 7, by using a direct current energizing device 63 to apply positive to the third electrode terminal 35 and negative to the negative electrode terminal 33, the movement of lithium from the lithium metal 41 to the negative electrode is accelerated. The storage time can be greatly shortened.

  Further, as shown in FIG. 8, a constant voltage circuit 65 is connected between the positive electrode terminal 31 and the third electrode terminal 35, and the shunt current Is is applied only when the voltage between both terminals 31-35 exceeds a predetermined voltage Vs. By performing parallel voltage control for energization, it is possible to prevent the electrolyte from being decomposed due to the potential of the positive electrode becoming too high. Thereby, it is possible to reliably suppress gas generation caused by the potential of the positive electrode becoming too high during charging or charging / discharging in series connection.

  In this case, the lithium metal 41 is preferably installed in a larger amount than is necessary for pre-occlusion in the negative electrode. The constant voltage circuit 65 can be configured using an active circuit such as a voltage detection circuit or a passive element such as a Zener diode.

  A rectangular sheet-like positive electrode portion in which a positive electrode capable of reversibly carrying lithium ions or anions is formed on a sheet-like positive electrode current collector, and a negative electrode electrode capable of occluding and releasing lithium ions are provided for the sheet-like negative electrode collector. A rectangular sheet-shaped negative electrode portion formed on the electric current body is alternately laminated with a separator interposed therebetween, and an external body connected to the positive electrode current collector and the negative electrode current collector, respectively. This is a lithium ion storage / release type organic electrolyte storage battery equipped with a terminal, which makes it possible to smoothly and quickly perform the preliminary storage of lithium ions into the negative electrode, and the frequency of handling lithium metal in the production process. It can be reduced to increase productivity.

  Further, it is possible to reliably suppress gas generation due to decomposition of the electrolytic solution due to the potential of the positive electrode becoming too high during charging or charging / discharging in series connection.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view and a top view of an essential part showing a first embodiment of a lithium ion storage / release type organic electrolyte storage battery according to the present invention. It is the top view which expand | deployed the layer of the laminated electrode body, and sectional drawing which shows a lamination | stacking state. It is principal part sectional drawing which shows 2nd Embodiment of the lithium ion storage-release organic electrolyte storage battery by this invention. It is principal part sectional drawing which shows 3rd Embodiment of the lithium ion storage-release type organic electrolyte storage battery by this invention. It is principal part sectional drawing which shows 4th Embodiment of the lithium ion occlusion / release organic electrolyte storage battery by this invention. It is principal part sectional drawing and top view which show 5th Embodiment of the lithium ion occlusion / release type organic electrolyte storage battery by this invention. It is a top view which shows typically the method of performing preocclusion using a 3rd electrode terminal. It is a top view which shows typically the structure which prevents gas generation | occurrence | production using a 3rd electrode terminal.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Element container 20 Stacked electrode body 21 Positive electrode part 211 Positive electrode 212 Current collector 213 Conductive lead part 22 Separator 23 Negative electrode part 231 Negative electrode 232 Current collector 233 Conductive lead part 25 Conductor 31 Positive electrode terminal 33 Negative electrode terminal 35 3rd electrode Terminal 41 Lithium metal 52 Through-hole 521 Hole 61 Jumper conductor 63 DC energizing device 65 Constant voltage circuit 71 Liquid-permeable insulating layer 72 Liquid-permeable insulator

Claims (4)

A rectangular sheet-like positive electrode portion in which a positive electrode capable of reversibly carrying lithium ions or anions is formed on a sheet-like positive electrode current collector, and a negative electrode electrode capable of occluding and releasing lithium ions are provided for the sheet-like negative electrode collector. A rectangular sheet-shaped negative electrode portion formed on the electric current body is alternately laminated with a separator interposed therebetween, and an external body connected to the positive electrode current collector and the negative electrode current collector, respectively. A lithium ion storage / release type organic electrolyte storage battery with a terminal,
A through hole extending in the stacking direction is formed in the laminated electrode body, and lithium metal for preliminarily occluding lithium ions in the negative electrode is loaded into the through hole, and the lithium metal is placed in the outermost layer of the laminated electrode body. Lithium ion storage / release organic electrolyte storage battery characterized in that the lithium metal is conductively connected to a negative electrode on the inside or outside of the storage battery through conductive connection to the disposed conductor. .   2. The lithium ion occlusion / release organic electrolyte according to claim 1, wherein a third electrode terminal is provided as an external terminal separately from the positive electrode terminal and the negative electrode terminal, and the third electrode terminal is connected to the conductor. Storage battery.   3. The lithium ion storage / release type organic electrolyte storage battery according to claim 2, further comprising a constant voltage circuit in which a voltage between the third electrode terminal and the positive electrode terminal is equal to or lower than a predetermined value.   4. The lithium ion storage / release type organic electrolyte storage battery according to claim 1, wherein a liquid-permeable insulating layer is interposed between the inner wall surface of the through hole and the lithium metal.

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