JP2013016286A - Thin film lithium secondary battery formation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for forming a lithium secondary battery under a dry environment.SOLUTION: A thin film lithium secondary battery formation device 1 has: a movement chamber 2 formed into a shape having a longitudinal direction; an inlet door 81 and an outlet door 82 provided at one end and the other end in the longitudinal direction of the movement chamber 2, and capable of connecting and blocking atmospheric air and the movement chamber 2; a moving mechanism arranged in the movement chamber 2, and moving a substrate 70 carried in the movement chamber 2 from an upstream side to a downstream side while the inlet door 81 side is upstream and the outlet door 82 side is downstream; and a plurality of partition devices 83 provided in a moving direction of the substrate in the movement chamber 2, and serially parting the movement chamber 2 into plural regions between the inlet door 81 and the outlet door 82. A gas introduction device 55 for making an internal atmosphere of the movement chamber 2 into a rare gas atmosphere is connected to the movement chamber 2 between the inlet door 81 and the outlet door 82. Rare gas is introduced inside the movement chamber 2 by the gas introduction device 55, so as to form a lithium secondary battery under a dry environment.

Description

  The present invention relates to a technique for producing a thin film lithium secondary battery in a dry environment using an integrated device.

Lithium secondary batteries are widely used as rechargeable batteries for mobile phones and notebook computers, but lithium secondary batteries using a solid electrolyte that does not cause leakage of the electrolyte are attracting attention.
Since lithium constituting the lithium secondary battery easily reacts with moisture, a manufacturing apparatus is arranged in a dry room having a dew point temperature of about −50 ° C., and an operator wears protective clothing.

  If the moving chambers in which the substrates move are connected by boxes having the same atmosphere, a dry room or the like is unnecessary, but the processing chambers are not divided for each processing apparatus. When trouble occurs in one processing equipment during production, if the processing equipment in which the trouble has occurred is exposed to the air to maintain it, the substrate processed by other processing equipment is also exposed to the air. It was.

JP 2008-282731 A

  The present invention was created to solve the above-described disadvantages of the prior art. The purpose of the present invention is to provide a lithium secondary battery in a dry environment by introducing a rare gas into a moving chamber in the production of a lithium secondary battery. Is to provide a technology for forming

In order to solve the above problems, the present invention provides a positive electrode film made of a metal containing lithium, a positive electrode current collector film in contact with the positive electrode film, and a solid containing lithium disposed on the positive electrode film A thin film lithium secondary battery for manufacturing a thin film lithium secondary battery, comprising: a solid electrolyte film made of an electrolyte; a negative electrode film disposed on the solid electrolyte film; and a negative electrode current collector film in contact with the negative electrode film. A secondary battery forming device, a moving chamber formed in a shape having a longitudinal direction, provided at one end and the other end of the moving chamber in the longitudinal direction, and connected between the atmosphere and the moving chamber The loading chamber and the unloading chamber that can be shut off are arranged in the moving chamber, and the substrate loaded in the moving chamber is moved from the upstream to the downstream with the loading chamber side as the upstream and the unloading chamber side as the downstream. The moving mechanism and the moving chamber include A solid electrolyte membrane forming apparatus for forming a solid electrolyte membrane and a negative electrode film forming device for forming the negative electrode film are connected in this order from the loading / unloading chamber side toward the unloading chamber side, and the solid electrolyte The portion of the moving chamber where the film forming apparatus and the negative electrode film forming apparatus are connected is a thin film lithium secondary battery forming apparatus configured to be hermetically sealed by an openable / closable partition device.
According to the present invention, the thin film lithium secondary battery has a protective film on the negative electrode film, and the protective film forming apparatus for forming the protective film is the negative electrode film forming apparatus of the transfer chamber. A thin-film lithium secondary battery forming apparatus connected to a position between a connected portion and a portion to which the carry-out chamber is connected.
Further, the present invention provides a positive electrode film formation in which the positive electrode film is formed in a portion between the moving chamber and a portion where the solid electrolyte membrane forming apparatus is connected and a portion where the carry-in chamber is connected. A thin-film lithium secondary battery forming apparatus to which the apparatus is connected.
Further, the present invention provides the positive electrode current collector film, wherein the positive electrode current collector film is formed between a portion where the positive electrode film forming apparatus is connected to the moving chamber and a portion where the carry-in chamber is connected. A thin-film lithium secondary battery forming apparatus to which a forming apparatus is connected.
In the present invention, the negative electrode current collector film is disposed in a portion between the moving chamber and a portion where the solid electrolyte membrane forming device is connected and a portion where the negative electrode film forming device is connected. A thin-film lithium secondary battery forming apparatus to which a negative electrode current collector film forming apparatus to be formed is connected.
Moreover, this invention is a thin film lithium secondary battery formation apparatus with which the carrying in / out chamber which carries out the said board | substrate in the said movement chamber was provided in the position between the said carrying in chamber and the said carrying out chamber of the said moving chamber.

  According to the present invention, when manufacturing a lithium secondary battery, it is not necessary to expose lithium to the atmosphere, and lithium secondary batteries can be produced consistently in a dry atmosphere.

Configuration diagram of lithium secondary battery integrated device Configuration diagram of lithium secondary battery mass production equipment (A): Plan view of thin-film lithium secondary battery (b): A-A 'cut cross-sectional view of thin-film lithium secondary battery

Reference numeral 1 in FIG. 1 is a lithium secondary battery integrated device capable of producing a thin film lithium secondary battery, and has an elongated moving chamber 2.
On the side surface of the moving chamber 2, a positive electrode current collector film forming device 7, a positive electrode film forming device 8, an electrolyte film forming device 9, a negative electrode current collector film forming device 10, and a negative electrode film forming device 11 , The protective film forming apparatus 12 is connected via the first to sixth charging / extracting chambers 23 ₁ to 23 ₆ , the connecting portions of the devices 9 to 12 of the moving chamber 2, and the moving chamber 2 At both ends, a partition device 83 is provided and divided.
The loading chamber 31 is connected to one end of the moving chamber 2 in the longitudinal direction via a partition device 83, and the unloading chamber 32 is similarly connected to the other end via a partition device 83.
An entrance door 81 is provided between the carry-in chamber 31 and the atmosphere, and an exit door 82 is provided between the carry-out chamber 32 and the atmosphere.

A moving mechanism (not shown) is arranged in the moving chamber 2, and the substrate can be moved inside the moving chamber 2.
Since a plurality of partition devices 83 are provided from the upstream side to the downstream side in the moving chamber 2, the inside of the moving chamber 2 is divided into a plurality of regions in series between the entrance door 81 and the exit door 82. .

  The partition device 83 is a vacuum valve, is configured to be openable and closable, and is configured to connect or block an upstream region and a downstream region of the partition device 83. Of the partition device 83, the portion sandwiched between the partition device 83 positioned at the uppermost stream and the entrance door 81 is the carry-in chamber 31, and the partition device 83 and the exit door 82 positioned at the most downstream side in the substrate transport direction. Between these is the carry-out chamber 32.

A gas introducing device 55 that can make the internal atmosphere of the moving chamber 2 a gas atmosphere is connected to the portion of the moving chamber 2 between the carry-in chamber 31 and the carry-out chamber 32. Here, the gas is a rare gas having a dew point temperature of −60 ° C. or more and −50 ° C. or less, and argon gas is used.
When the substrate is processed in the moving chamber 2, the inside of the moving chamber 2 is in an atmosphere of argon gas introduced by the gas introducing device 55. The gas introduced into the moving chamber 2 is discharged from the moving chamber 2 to the outside by the gas discharge device 56. Further, a circulation device (not shown) is provided between the gas discharge device 56 and the gas introduction device 55, and the rare gas discharged from the gas discharge device 56 is returned to the gas introduction device 55 and introduced into the moving chamber 2. You may do it.

  The partition devices 83 at both ends of the moving chamber 2 are closed, and the internal atmosphere of the carry-in chamber 31 and the internal atmosphere of the carry-out chamber 32 are shielded from the internal atmosphere of the moving chamber 2, and in this state, the entrance door 81 and the exit door 82. Is opened, the internal atmosphere of the carry-in chamber 31 and the internal atmosphere of the carry-out chamber 32 can be connected to the atmosphere while maintaining the inside of the moving chamber 2 in a desired gas atmosphere. At this time, the substrate can be carried into the carry-in chamber 31 from the atmosphere side, and the substrate in the carry-out chamber 31 can be carried out to the atmosphere. Reference numeral 70 denotes a substrate that is carried in, and reference numeral 71 denotes a substrate that is carried out.

Next, the entrance door 81 and the exit door 82 are closed, and the atmosphere inside the carry-in chamber 31 and the carry-out chamber 32 is shut off from the atmospheric atmosphere.
An evacuation system 54 ₁ , 54 ₂ and a gas introduction system 51 ₁ , 51 ₂ are connected to the carry-in chamber 31 and the carry-out chamber 32, respectively. 54 ₁ and 54 ₂ are operated to make the internal atmosphere of the carry-in chamber 31 and the carry-out chamber 32 a vacuum atmosphere, and the gas introduction device 51 ₁ , 51 ₂ introduces a gas introduction device into the carry-in chamber 31 and the carry-out chamber 32. When the same gas as the gas introduced by 55 is introduced, the internal atmosphere of the carry-in chamber 31 and the carry-out chamber 32 can be made the same gas atmosphere as the internal atmosphere of the moving chamber 2.

  When the carry-in chamber 31 and the carry-out chamber 32 have the same gas atmosphere as the moving chamber 2, the substrate 70 can be carried into the moving chamber 2 from the carrying-in chamber 31 and the substrate can be carried out from the moving chamber 2 into the carry-out chamber 32. it can.

  Among the front chambers 88 to 92, which are portions separated by the partition device 83 of the moving chamber 2, the first front chamber 88 closest to the carry-in chamber 31 includes the positive electrode current collector film forming device 7 and the positive electrode film forming device. 8, and the second to fifth front chambers 89 to 92 that are adjacent to the first front chamber 88 in order are provided with an electrolyte film forming device 9, a negative electrode current collector film forming device 10, and a negative electrode. The electrode film forming apparatus 11 and the protective film forming apparatus 12 are connected one by one in this order.

The first to sixth charge ejecting chamber 23 _{1-23 6,} the evacuation system 61 _{1-61 6} respectively, and a gas introduction system 52 _{1-52 6} for introducing the same gas as the gas introduction device 55 connected Has been.

By blocking the respective inner atmosphere of moving chamber 2 and the internal atmosphere of the first to sixth charge ejecting chamber 23 _{1-23 6,} first to sixth charge take-out by operating the evacuation system 61 _{1-61 6} after the vacuum atmosphere inside atmosphere of the chamber 23 _{1-23 6,} to operate the gas introduction system 52 _{1-52 6,} moving chamber 2 and the internal atmosphere of the first to sixth charge ejecting chamber 23 _{1-23 6} When the atmosphere is the same as the internal atmosphere, the substrate can be moved between the first to fifth front chambers 88 to 92 and the first to sixth preparation take-out chambers 23 ₁ to 23 ₆ .

Vacuum exhaust systems 53 _{1 to} 53 ₆ are connected to the film forming apparatuses 7 to 12, respectively. While the substrate is being processed in each of the film forming apparatuses 7 to 12, the moving chamber 2 is placed in a gas atmosphere at a normal pressure, whereas the first to sixth charging / discharging chambers 23 ₁ to 23 are used. ₆ and the film forming apparatuses 7 to 12 are placed in a vacuum atmosphere.

When the first to sixth charging / discharging chambers 23 ₁ to 23 ₆ have the same gas atmosphere as the moving chamber 2, the internal atmosphere of the first to sixth charging / discharging chambers 23 ₁ to 23 ₆ is set to the film forming apparatus 7 to It is cut off from 12 internal atmospheres.
The first to sixth charge ejecting chamber 23 _{1-23 6,} each of the internal atmosphere isolated from the atmosphere inside the mobile chamber 2, when operating the evacuation system 61 _{1-61 6,} the first to sixth The internal atmosphere of each of the charging / extracting chambers 23 ₁ to 23 ₆ can be made a vacuum atmosphere. When the insides of the first to sixth charging / unloading chambers 23 ₁ to 23 ₆ are in a vacuum atmosphere, they can be connected to the internal atmospheres of the respective film forming apparatuses 7 to 12, and the substrate can be transferred therebetween.

At that time, in the film forming apparatus 7-12, it can be returned to the first to sixth charge ejecting chamber 23 _{1-23 6} was vacuum processing a substrate inside.
When the substrate 70 is vacuum-processed by the lithium secondary battery integrated apparatus 1, the moving chamber 2 is set to a rare gas atmosphere, and the insides of the first to sixth charging / discharging chambers 23 ₁ to 23 ₆ are set to a vacuum atmosphere.

  Next, the partition device 83 of the carry-in chamber 31 is opened so that the atmosphere is maintained without mixing air, and the substrate 70 in the carry-in chamber 31 is moved from the carry-in chamber 31 to the first front chamber 88 of the moving chamber 2. Then, the opened partitioning device 83 is closed. The partition device 83 opens and closes when the substrate 70 is moved.

The substrate carried into the first front chamber 88 is moved from the first front chamber 88 to the positive electrode current collector film forming apparatus 7 through the first loading / unloading chamber 23 ₁ , and the positive electrode current collector film in forming apparatus within 7, after forming the thin film (positive electrode collector layer) on the substrate surface, through the first feed ejecting chamber 23 _1, back to the first front chamber 88, the first front chamber 88 Is moved to the downstream side and carried into the positive electrode film forming apparatus 8 via the second preparation / extraction chamber 23 ₂ .
In the positive electrode film forming apparatus 8, a thin film (positive electrode film) is formed on the surface of the thin film (positive electrode current collector film) formed in the positive electrode current collector film forming apparatus 7 in contact with the thin film.

Subsequently, it returns to the 1st front chamber 88 via the _2nd preparation taking-out chamber 232, and moves to the downstream in the 1st front chamber 88. FIG.
An annealing chamber 6 is connected to the first front chamber 88, and a substrate is carried into the annealing chamber 6 and heat treatment is performed.
After the heat treatment, the substrate is returned from the annealing chamber 6 into the first front chamber 88, the partition device 83 is opened, the substrate is moved from the first front chamber 88 to the second front chamber 89, and the second to fifth chambers are moved. The electrolyte film forming device 9, the negative electrode current collector film forming device 10, the negative electrode film forming device 11, and the protective film forming device 12 connected to the front chamber are carried in and out in this order, Within each chamber 9-12, an electrolyte membrane, a negative electrode current collector film, a negative electrode film in contact with the electrolyte membrane and the negative electrode current collector film, and a protective film are formed in this order. Portions other than part of the negative electrode current collector film and the positive electrode current collector film are covered with a protective film.

After forming each thin film on the substrate, the substrate is moved to the carry-out chamber 32. Reference numeral 71 denotes a substrate moved into the carry-out chamber 32. Next, after closing the partition device 83 between the carry-out chamber 32 and the moving chamber 2 (the fifth front chamber 92), the outlet door 82 is opened to take out the substrate 71 to the atmosphere.
As described above, the lithium secondary battery can be manufactured without being exposed to the atmosphere until the protective film is formed from the positive electrode current collector film.

3A and 3B show a lithium secondary battery 73 manufactured by the lithium secondary battery integrated device 1 of the present invention.
By the above procedure, the positive electrode current collector film 41 made of Pt and Ti or Cr is formed on the surface of the substrate 40 made of glass, silicon, or mica by the positive electrode current collector film forming apparatus 7. Then, the positive electrode film 42 was formed on the surface of the positive electrode current collector film 41 by the positive electrode film forming apparatus 8. The positive electrode film 42 is a thin film made of any one layer of a LiCoO ₂ film, a LiNiO ₂ film, a LiMnO ₂ film, and a LiFePO ₄ film.

Next, after annealing the substrate 40 having the positive electrode film 42 formed on the surface in the annealing chamber 6, the electrolyte film forming apparatus 9 forms an electrolyte film 43 made of LiPON so as to cover the surface of the positive electrode film 42. did.
Next, the negative electrode current collector film forming apparatus 10 is configured so that a part of the negative electrode current collector film 44 made of a metal of Cu or Ni is placed on the electrolyte film 43 on the electrolyte film 43. Next, the negative electrode film forming apparatus 11 forms a negative electrode film 45 containing Li on the electrolyte film 43 so as to partially contact the negative electrode current collector film 44. Here, it formed by the vapor deposition method. Here, the negative electrode film 45 is made of lithium.

Next, the protective film forming apparatus 12 forms a protective film 46 on the surface of the negative electrode film 45 to expose a part of the positive electrode current collector film 41 and a part of the negative electrode current collector film 44. Was covered with a protective film 46 to form a thin film lithium secondary battery 73.
Here, the protective film 46 is a laminated film in which an Al ₂ O ₃ film, an Al film, and an Al ₂ O ₃ film are laminated in this order from the lower layer, but a polyurea film may be formed as the protective film 46. Good.
The protective film 46 is not limited to a metal or a metal oxide, and may be an organic or inorganic material as long as moisture is protected from lithium.

  Moreover, the lithium secondary battery integrated device 1 of the present invention forms the above-described thin film lithium secondary battery even if one of the positive electrode current collector film forming device 7 and the negative electrode current collector film forming device 10 is reduced. can do.

The lithium secondary battery mass production apparatus 50 in FIG. 2 is an apparatus when the positive electrode current collector film forming apparatus 7 is reduced from the lithium secondary battery integrated apparatus 1 in FIG. The carry-in / out chamber 36 is connected to the third front chamber 90 to which the negative electrode current collector film forming apparatus 10 is connected.
The carry-in / out chamber 36 can move the substrate between the third front chamber 90 and the carry-in / out chamber 36 while maintaining the gas atmosphere inside the third front chamber 90. The substrate can be moved between the loading / unloading chamber 36 and the atmosphere while maintaining the gas atmosphere inside the chamber 90.

In the negative electrode current collector film forming apparatus 10, a target for forming the positive electrode current collector film 41 and a target for forming the negative electrode current collector film 44 are separately arranged.
First, the positive electrode film 42 is formed on the substrate carried in from the carry-in chamber 31 by the positive electrode film forming apparatus 8. Then, the substrate is moved to the negative electrode current collector film forming apparatus 10, this by the negative electrode current collector film forming apparatus 10 to form a positive electrode collector layer 41, it is moved to the fourth loading ejecting chamber 23 _4.

The carry-in / out chamber 36 is disposed at a position facing the _fourth charging / discharging chamber 234 of the negative electrode current collector film forming apparatus 10, and the fourth charging / discharging chamber 36 is not returned to the upstream side without returning the inside of the moving chamber 2 to the upstream side. 23 ₄ is moved to the transport room 36 from maintaining the gas atmosphere in the moving chamber 2, taken in the atmosphere.
The substrate taken out to the atmosphere is carried from the carry-in chamber 31 into the moving chamber 2, annealed in the annealing chamber 6, moved into the electrolyte film forming apparatus 9, and the electrolyte film 43 is formed.
The substrate on which the electrolyte film 43 is formed is moved to the negative electrode current collector film forming apparatus 10 to form the negative electrode current collector film 44. Then, the negative electrode film forming apparatus 11 and the protective film forming apparatus 12 are An electrode film 45 and a protective film 46 are formed to constitute a lithium secondary battery, which is taken out from the carry-out chamber 32 to the atmosphere.

Thus, according to the lithium secondary battery mass production apparatus 50, when the thin film is formed on the substrate surface, after the substrate carried into the moving chamber 2 from the carry-in chamber 31 is taken out from the carry-in / out chamber 36 to the atmosphere, The film can be returned to the carry-in chamber 31 and moved again in the moving chamber 2 to form a thin film.
In addition, if the board | substrate in which the thin film was formed is carried in from the carrying in / out chamber 36, another thin film formation chamber can also be abbreviate | omitted. In short, in the present invention, even if a carry-out chamber (including the carry-in / out chamber 36) is provided at any position of the moving chamber 2, any of the film forming apparatuses 7 to 12 can be omitted. The position facing one of the film forming apparatuses 7 to 12 is good so that the substrate does not flow backward in the moving chamber.

  In the case where the positive electrode current collector film 41 and the negative electrode current collector film 44 do not cross each other, it is possible to reduce the negative electrode current collector film forming device 10 from the lithium secondary battery integrated device 1. In the lithium secondary battery integrated device 1 in the arrangement of FIG. 1, when the negative electrode current collector film forming device 10 is not provided, a target for forming the positive electrode current collector film 41 inside the positive electrode current collector film forming device 7 Then, a target for forming the negative electrode current collector film 44 is arranged, and the substrate on which the positive electrode current collector film 41 and the positive electrode film 42 are formed is taken out from the carry-in / out chamber to the atmosphere and annealed, and then the positive electrode current collector film forming apparatus 7, the negative electrode current collector film 44 is formed, the electrolyte film forming apparatus 9 forms the electrolyte film 43, the negative electrode film forming apparatus 11 forms the negative electrode film 44 made of lithium metal, and the protective film forming apparatus 12 may form the protective film 46.

  In the above-described process, the transport mechanism is configured by a large number of rollers and belts arranged close to each other, and in order for the substrate to move on the transport mechanism, the substrate may be placed on a tray.

2 ... Moving chamber 7 ... Positive electrode current collector film forming device 8 ... Positive electrode film forming device 9 ... Electrolyte film forming device 10 ... Negative electrode current collector film forming device 11 ... Negative electrode film forming device 12 ... ... Protective film forming apparatus 23 ₁ to 23 ₆ ...... First to sixth charging / unloading chambers

Claims (6)

A positive electrode film made of a metal containing lithium;
A positive electrode current collector film in contact with the positive electrode film;
A solid electrolyte membrane comprising a solid electrolyte containing lithium disposed on the positive electrode membrane;
A negative electrode membrane disposed on the solid electrolyte membrane;
A negative electrode current collector film in contact with the negative electrode film;
A thin film lithium secondary battery forming apparatus for manufacturing a thin film lithium secondary battery having
A moving chamber formed in a shape having a longitudinal direction;
A loading chamber and a unloading chamber which are provided at one end and the other end in the longitudinal direction of the moving chamber, respectively, and can be connected and disconnected between the atmosphere and the moving chamber;
A moving mechanism that is arranged in the moving chamber and moves the substrate loaded into the moving chamber from the upstream to the downstream, with the loading chamber side as the upstream, the unloading chamber side as the downstream, and
In the moving chamber, a solid electrolyte membrane forming device that forms a solid electrolyte membrane and a negative electrode membrane forming device that forms the negative electrode membrane in this order from the carry-in chamber side toward the carry-out chamber side. A thin-film lithium secondary battery configured such that a portion of the moving chamber connected to the solid electrolyte membrane forming apparatus and the negative electrode film forming apparatus is hermetically sealed by an openable / closable partition device Forming equipment. The thin film lithium secondary battery has a protective film on the negative electrode film,
The protective film forming apparatus for forming the protective film is connected to a position between a portion of the moving chamber connected to the negative electrode film forming device and a portion connected to the carry-out chamber. The thin film lithium secondary battery forming apparatus described.   A positive electrode film forming device for forming the positive electrode film is connected to the moving chamber between a portion to which the solid electrolyte membrane forming device is connected and a portion to which the carry-in chamber is connected. The thin film lithium secondary battery formation apparatus of any one of Claim 1 or Claim 2.   Connected to the moving chamber is a cathode current collector film forming apparatus that forms the cathode current collector film between a portion to which the positive electrode film forming apparatus is connected and a portion to which the carry-in chamber is connected. The thin film lithium secondary battery forming apparatus according to claim 3.   A negative electrode current collector that forms the negative electrode current collector film in a portion between the moving chamber and a portion connected to the solid electrolyte membrane forming device and a portion connected to the negative electrode film forming device. The thin film lithium secondary battery forming apparatus according to any one of claims 1 to 4, wherein a film forming apparatus is connected.   6. The thin film lithium secondary battery according to claim 1, wherein a loading / unloading chamber for unloading the substrate in the moving chamber is provided at a position between the loading chamber and the unloading chamber of the moving chamber. Next battery forming device.

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