JP5247570B2 - Thin film lithium secondary battery manufacturing apparatus and thin film lithium secondary battery manufacturing method - Google Patents

Description

  The present invention relates to a technique for manufacturing a lithium secondary battery using a solid electrolyte, and more particularly to a technique for manufacturing a lithium secondary battery using a thin film in a vacuum.

Conventionally, lithium ion secondary batteries have been widely known as power sources for mobile phones and personal computers.
However, since a lithium ion secondary battery uses a liquid electrolyte, liquid leakage, ignition, etc. may occur, and there are safety issues.
Therefore, in recent years, an all-solid-state lithium secondary battery using a solid material as an electrolyte material has been proposed, and its development is progressing.
In particular, as an all-solid-state lithium secondary battery using a solid material, an all-solid-type lithium secondary battery including a thin film is expected as a power source for a card-type electronic component or the like.
However, an all-solid-state lithium secondary battery made of a thin film is manufactured through various processes, and thus there is a problem that the manufacturing apparatus becomes large and complicated.
In addition, as a prior art document relevant to this invention, there exist the following, for example.

JP 2002-42863 A

  The present invention has been made in view of the problems of the conventional technology, and an object of the present invention is to provide a technology for manufacturing a thin film lithium secondary battery with a vacuum device having a small and simple configuration. is there.

The present invention has been made to solve the above-described problems. A thin film lithium secondary battery having a positive electrode layer, a negative electrode layer, a solid electrolyte layer, a positive electrode current collecting layer, a negative electrode current collecting layer, and a protective layer on a substrate in a vacuum. A thin-film lithium secondary battery manufacturing apparatus for manufacturing a substrate, a loading / unloading chamber for loading and unloading the substrate, and a positive electrode layer for forming a positive electrode layer containing lithium in the molecule on the substrate by sputtering A forming chamber, a negative electrode layer forming chamber for forming a negative electrode layer on the substrate by vacuum deposition, a solid electrolyte layer forming chamber for forming a solid electrolyte layer containing lithium in the molecule on the substrate by sputtering, and the substrate A current collector layer forming chamber for forming a positive electrode current collecting layer and a negative electrode current collecting layer by sputtering and a protective layer forming chamber for forming a protective layer on the substrate are arranged around a transport chamber having a substrate transport mechanism. Thin-film lithium secondary battery manufacturing apparatus, each of which is arranged and connected to the transfer chamber, and is provided with substrate heating means for annealing the positive electrode layer formed on the substrate in the charging / unloading chamber It is.
In the present invention, the negative electrode layer forming chamber is also effective when a substrate reversing mechanism for reversing the vertical relationship of the substrates in a vacuum is provided.
The present invention is also effective when a mask exchange mechanism for exchanging the film forming mask is provided in the current collector layer forming chamber.
On the other hand, the present invention is a method of manufacturing a thin film lithium secondary battery using any one of the above-described thin film lithium secondary battery manufacturing apparatuses, wherein the current collector layer forming chamber is provided for forming a current collector layer. A plurality of targets including a target and a target for forming a protective layer are arranged, and the substrate carried in from the charging / unloading chamber is carried into the current collector layer forming chamber via the transfer chamber, and the positive electrode collector is placed on the substrate. A step of forming an electric layer by sputtering, a step of carrying the substrate into the charging / unloading chamber through the transfer chamber, and annealing the positive electrode current collecting layer on the substrate; and the substrate through the transfer chamber. Carrying the positive electrode layer forming chamber into the positive electrode layer forming chamber and forming the positive electrode layer on the substrate by sputtering; and carrying the substrate into the solid electrolyte layer forming chamber through the transfer chamber and placing the substrate on the substrate. A step of forming a body electrolyte layer by sputtering, a step of carrying the substrate into the negative electrode layer forming chamber via the transfer chamber, and forming the negative electrode layer on the substrate by vacuum deposition; and the transfer of the substrate Carrying the current collector layer forming chamber through a chamber and forming the negative electrode current collecting layer on the substrate by sputtering; and carrying the substrate into the protective layer forming chamber through the transfer chamber. Forming a first protective layer on the substrate by vapor deposition polymerization; carrying the substrate into the current collector layer forming chamber through the transfer chamber; and forming a first protective layer on the first protective layer on the substrate. A method for producing a thin film lithium secondary battery comprising: a step of laminating and forming two protective layers by sputtering.
In the present invention, when forming the negative electrode layer, it is also effective in the case of having a step of inverting the vertical relation of the substrate by the substrate inverting mechanism.
In the present invention, when forming the positive electrode current collecting layer, the negative electrode current collecting layer, and the second protective layer, it is also effective in the case of having a step of replacing the film forming mask by the mask replacing mechanism. is there.
In the present invention, it is particularly effective when the positive electrode layer is made of lithium cobalt oxide.
In the present invention, it is particularly effective when the solid electrolyte layer is made of lithium phosphate oxynitride.

In the case of the apparatus of the present invention, the charging / unloading chamber, the positive electrode layer forming chamber, the negative electrode layer forming chamber, the solid electrolyte layer forming chamber, the current collector layer forming chamber, and the protective layer forming chamber have a substrate transport mechanism. Since the substrate heating means is disposed in the periphery of the transfer chamber and connected to the transfer chamber, and the substrate heating means is provided in the charging / unloading chamber, the thin film lithium secondary can be used in a vacuum apparatus having a small number of film forming chambers and processing chambers. A battery can be manufactured.
Further, according to the present invention, since the annealing process can be performed in a time during which the preparation / extraction chamber is not used, each process can be performed efficiently.
In the present invention, when a substrate reversing mechanism for reversing the vertical relationship of the substrate in a vacuum is provided in the negative electrode layer forming chamber, the substrate is reversed by this substrate reversing mechanism, so that vacuum deposition is performed with a so-called face up. There is no need to use a specially configured apparatus, and as a result, the cost can be reduced by using a general vacuum deposition apparatus.
In addition, in the case where a mask exchange mechanism for exchanging the film formation mask is provided in the current collector layer forming chamber, the film formation mask is exchanged by this mask exchange mechanism, so that different materials can be used easily. A current collector layer can be stacked.
Further, when a material containing a metal such as aluminum is used as the material of the protective layer, the protective layer can be formed by sputtering in the current collector layer forming chamber, so that a simple configuration without increasing the film forming chamber is possible. A thin film lithium secondary battery manufacturing apparatus can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the technique which manufactures a thin film lithium secondary battery with the vacuum apparatus of a small and simple structure can be provided.

Schematic configuration plan view of an embodiment of a thin-film lithium secondary battery manufacturing apparatus according to the present invention The longitudinal cross-sectional view which shows the internal structure of the preparation taking-out chamber and transfer chamber in the embodiment (A) (b): Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 1) (A) (b): Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 2) (A) (b): Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 3) (A) (b): Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 4) (A) (b): Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 5) Explanatory drawing which shows the conveyance operation of the board | substrate in the manufacturing process of the thin film lithium secondary battery of the embodiment (the 6)

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic configuration plan view of an embodiment of a thin-film lithium secondary battery manufacturing apparatus according to the present invention.
As shown in FIG. 1, the thin-film lithium secondary battery manufacturing apparatus 1 of the present embodiment includes a transfer chamber 2 having a hexagonal cross section connected to a vacuum exhaust system (not shown). A transfer robot 3 for transferring the substrate 10 is disposed.
This transfer robot 3 has an arm 30 that can be freely extended and retracted, and a carrier 31 for supporting and transferring the substrate 10 is attached to the tip of the arm 30.
Around the transfer chamber 2, a charging / unloading chamber 4 that also serves as an annealing chamber, first to third sputtering chambers 5, 6, 7, a negative electrode layer forming chamber 8, and a protective layer forming chamber 9 are provided.
Here, the charging / unloading chamber 4, the first to third sputtering chambers 5 to 7, the negative electrode layer forming chamber 8, and the protective layer forming chamber 9 are connected to a vacuum exhaust system (not shown) and gate valves 40 and 50, respectively. , 60, 70, 80, 90 are connected to the transfer chamber 2.
In the present embodiment, the charging / unloading chamber 4 also serves as an annealing chamber. In the charging / unloading chamber 4, as will be described later, for example, a lamp-heating heater (substrate heating means) 46 is provided. .

On the other hand, the first sputtering chamber 5 of the present embodiment also functions as a current collector layer forming chamber and a protective layer forming chamber, and there are a plurality of (four in the case of the present embodiment) inside. Targets 51 to 54 are arranged.
Examples of the first target 51 include a chromium (Cr) target for forming a positive electrode current collector layer, and examples of the second target 52 include a platinum (Pt) target for forming a positive electrode current collector layer, and a third target. As the target 53, for example, a copper (Cu) target for forming the negative electrode current collector layer is arranged, and as the fourth target 54, for example, an aluminum (Al) target for forming the protective layer is arranged.
In the first sputtering chamber 5, for example, a mask exchange mechanism for exchanging the film formation masks 56 (56 </ b> A, 56 </ b> B, 56 </ b> C) on the side thereof according to each sputtering process and mounting them at predetermined positions. 55 is provided.

The first sputtering chamber 5 of the present embodiment is connected to a reaction gas source (not shown), and is configured to introduce oxygen (O ₂ ) gas into the first sputtering chamber 5.
In the second sputtering chamber 6, for example, a lithium cobaltate (LiCoO ₂ ) target is disposed as the target 61 for forming the positive electrode layer.
In the third sputtering chamber 7, for example, a lithium phosphate (Li ₃ PO ₄ ) target is disposed as the target 71 for forming the solid electrolyte layer.
The third sputtering chamber 7 of the present embodiment is connected to a reaction gas source (not shown) and configured to introduce oxygen (O ₂ ) gas.
In the negative electrode layer forming chamber 8 of the present embodiment, an evaporation source 81 for heating and evaporating an evaporation material made of, for example, metallic lithium (Li) is disposed at the bottom.
The negative electrode layer forming chamber 8 is provided with a substrate reversing mechanism 82 that rotates, for example, the substrate 10 in a vacuum to reverse its vertical relationship.

In the protective layer forming chamber 9, for example, two types of raw material monomer evaporation sources 91 and 92 for forming a polyurea layer by vapor deposition polymerization are arranged.
In the case of the present invention, as a raw material monomer for vapor deposition polymerization, for example, 1,12-diaminododecane can be suitably used as a diamine monomer, and for example, 1,3-bis (isocyanatomethyl) cyclohexane can be suitably used as an isocyanate monomer. .

FIG. 2 is a longitudinal cross-sectional view showing the internal configuration of the charging / unloading chamber and the transfer chamber in the present embodiment.
As shown in FIG. 2, the charging / unloading chamber 4 of the present embodiment is provided with a charging / unloading port 42 for loading or unloading the substrate 10 at one side of the vacuum chamber body 41. 42 is configured to be sealed by an O-ring 44 with the openable / closable vacuum door 43 closed.
On the other hand, a substrate elevating mechanism 11 is provided in the lower part of the vacuum chamber body 41.
In the substrate lifting mechanism 11, a plurality of lifting pins 13 are provided on a base portion 12 provided below the vacuum chamber body 41, and these lifting pins 13 are inserted into the vacuum chamber body 41 and provided at respective upper ends. The substrate 10 is supported by the support portion 14.
Here, the substrate raising / lowering mechanism 11 has, for example, a ball screw 16 driven by a motor 15, and the base 12 is moved in the vertical direction by the operation of the ball screw 16.
On the other hand, a window portion 45 made of, for example, quartz glass is provided on the upper portion of the vacuum chamber body 41, and a lamp heater heater 46 is provided in a space above the window portion 45, for example.
In addition, a reflective surface 47 for reflecting infrared rays from the heater 46 is formed on the ceiling portion above the heater 46.

FIGS. 3A and 3B to 8 are explanatory views showing the substrate transport operation in the manufacturing process of the thin film lithium secondary battery of the present embodiment.
In order to manufacture the thin film lithium secondary battery in the present embodiment, as shown in FIGS. 2 and 3A, the vacuum door 43 of the charging / unloading chamber 4 is opened and the substrate 10 is loaded into the charging / unloading chamber 4. Then, it is placed on the support portion 14 of the substrate lifting mechanism 11.
Then, the substrate raising / lowering mechanism 11 is operated to place the substrate 10 at a predetermined height, and the vacuum door 43 of the loading / unloading chamber 4 is closed to perform evacuation.
After the pressure in the loading / unloading chamber 4 reaches a predetermined value, the gate valve 40 with the transfer chamber 2 is opened, and the transfer robot 3 is operated to insert the carrier 31 into the loading / unloading chamber 4 and lift the substrate. The mechanism 11 is lowered to place the substrate 10 on the carrier 31, and the gate valve 50 between the first sputtering chamber 5 and the first valve is opened. As shown in FIG. It is carried into the sputtering chamber 5.

In the first sputtering chamber 5, by applying a high frequency power between the substrate 10 and the first target 51 (for example, Cr) using the film formation mask 56 </ b> A for forming the positive electrode current collector layer, A Cr layer is formed on the substrate 10 by sputtering.
Thereafter, a positive current collecting layer (Pt / Cr) is formed on the substrate 10 by sputtering by applying high-frequency power to the second target 52 (for example, Pt).

Next, the transfer robot 3 is operated to load the substrate 10 into the second sputtering chamber 6 through the transfer chamber 2 as shown in FIG. Then, argon (Ar) gas is introduced into the second sputtering chamber 6, and high frequency power is applied between the substrate 10 and the target 61 (LiCoO ₂ ) for forming the positive electrode layer, whereby the positive electrode of the substrate 10. A positive electrode layer made of LiCoO ₂ is formed on the current collector layer.
In this step, sputtering is performed while the substrate 10 is heated by operating a heater (not shown) provided on the substrate stage.
Thereafter, the transfer robot 3 is operated, and the substrate 10 is carried into the preparation / extraction chamber 4 through the transfer chamber 2 as shown in FIG. Then, the heater 46 shown in FIG. 2 is operated to perform an annealing process on the positive electrode layer formed on the substrate 10 (for example, 600 ° C., about 10 minutes). Thereby, the positive electrode layer formed on the substrate 10 is crystallized.

Next, the transfer robot 3 is operated, and the substrate 10 is carried into the third sputtering chamber 7 through the transfer chamber 2 as shown in FIG. Then, for example, nitrogen (N ₂ ) gas is introduced into the third sputtering chamber 7 and high frequency power is applied between the substrate 10 and the solid electrolyte layer forming target 71 (Li ₃ PO ₄ ). A solid electrolyte layer made of LiPON (lithium phosphate oxynitride) is formed on the positive electrode layer of the substrate 10.
In this step, sputtering is performed while the substrate 10 is cooled by operating a cooling mechanism (not shown) provided on the substrate stage.

Next, the transfer robot 3 is operated, and the substrate 10 is carried into the first sputtering chamber 5 through the transfer chamber 2 as shown in FIG. Then, by applying high frequency power between the substrate 10 and the third target 53 (for example, Cu), a negative electrode current collector layer made of Cu is formed on the substrate 10 by sputtering.
In this step, the mask exchange mechanism 55 is operated to take out the film forming mask 56A for forming the positive electrode current collector layer from the first sputtering chamber 5, and the film forming mask 56B for forming the negative electrode current collector layer is removed. Sputtering is performed at a predetermined position.

Next, the transfer robot 3 is operated to carry the substrate 10 into the negative electrode layer forming chamber 8 through the transfer chamber 2 and heat the evaporation material (Li) of the evaporation source 81 as shown in FIG. Thus, a negative electrode layer made of Li is formed on the substrate 10 by vacuum deposition.
In this step, the substrate reversing mechanism 82 is operated to rotate the substrate 10, for example, thereby reversing the vertical relationship of the substrate 10 (so-called face down).
Then, a cooling mechanism (not shown) provided on the substrate stage is operated to perform vapor deposition while cooling the substrate 10.
Thereafter, the substrate reversing mechanism 82 is operated to rotate the substrate 10, thereby reversing the vertical relationship of the substrate 10 (so-called face up).

Next, the transport robot 3 is operated, and as shown in FIG. 6B, the substrate 10 is carried into the protective layer forming chamber 9, and the raw material monomers of the evaporation sources 91 and 92 are heated, thereby performing vapor deposition polymerization. A first protective layer made of polyurea is formed on the substrate 10.
The first protective layer made of polyurea formed by this vapor deposition polymerization has a property excellent in step coverage.
In this step, a temperature adjustment mechanism (not shown) provided on the substrate stage is operated to perform vapor deposition polymerization while maintaining the substrate 10 at a constant temperature.

Next, the transfer robot 3 is operated, and as shown in FIG. 7A, the substrate 10 is carried into the first sputtering chamber 5 through the transfer chamber 2, and oxygen, for example, is introduced into the first sputtering chamber 5. (O ₂ ) gas is introduced, and high frequency power is applied between the substrate 10 and the fourth target 54 (for example, Al) for forming the protective layer, whereby the first protective layer of the substrate 10 is applied. A second protective layer made of aluminum dioxide (Al ₂ O ₃ ) is formed by sputtering.
In this step, the mask exchange mechanism 55 is operated to take out the film-forming mask 56B for forming the positive electrode current collector layer from the first sputtering chamber 5, and the film-forming mask 56C for forming the protective layer is placed at a predetermined position. Sputtering is performed by attaching to the surface.
Thereby, the target all-solid-state thin film lithium secondary battery is obtained.
Thereafter, the substrate 10A on which the thin-film lithium secondary battery is formed is carried out of the thin-film lithium secondary battery manufacturing apparatus 1 through the loading / unloading chamber 4, as shown in FIGS.

As described above, in the case of the present embodiment, the loading / unloading chamber 4, the first to third sputtering chambers 5, 6, 7, the negative electrode layer forming chamber 8, and the protective layer forming chamber 9 are transport robots. Since the heater 46 is provided in each of the transfer chambers 2 and connected to the respective transfer chambers 2 and further in the charging / unloading chamber 4, there are few film forming chambers and processing chambers. A thin film lithium secondary battery can be manufactured with a vacuum apparatus.
Moreover, according to this Embodiment, since annealing treatment can be performed in the time which does not use the preparation taking-out chamber 4, each process can be performed efficiently.
Further, in the present embodiment, since the substrate reversing mechanism 82 for reversing the vertical relationship of the substrate 10 in the vacuum is provided in the negative electrode layer forming chamber 8, the substrate 10 is reversed by the substrate reversing mechanism 82. Therefore, it is not necessary to use an apparatus having a special configuration for performing vacuum deposition by so-called face-up, and as a result, the cost can be reduced by using a general vacuum deposition apparatus.

Further, since a mask exchange mechanism 55 for exchanging the film formation mask 56 is provided in the first sputtering chamber 5, a different material is used by exchanging the film formation mask 56 by the mask exchange mechanism 55. Thus, the current collector layer can be easily laminated.
Furthermore, in this embodiment, since aluminum dioxide (Al ₂ O ₃ ) is used as the material of the second protective layer, the second protective layer can be formed by sputtering in the first sputtering chamber 5, As a result, the thin film lithium secondary battery manufacturing apparatus 1 having a simple configuration can be obtained without increasing the number of film forming chambers.

The present invention is not limited to the above-described embodiment, and various changes can be made.
For example, in the above-described embodiment, as the protective layer, the first protective layer is formed by vapor deposition polymerization, and further, the second protective layer is formed on the first protective layer by sputtering. The present invention is not limited to this, and the protective layer can be formed only by sputtering.
In this case, a target made of Al (or Al ₂ O ₃ ) is used as the target, and a film in which, for example, Al ₂ O ₃ / Al / Al ₂ O ₃ is laminated can be formed as the protective layer. If such a protective layer is formed, the number of chambers in the vacuum chamber can be reduced and the moisture barrier property can be improved.
Furthermore, the arrangement configuration of each chamber in the above embodiment is merely an example, and can be appropriately changed according to a required process.
Furthermore, the present invention can be applied to substrates of various materials, shapes, and sizes, such as silicon substrates, ceramic substrates, heat resistant resin substrates, mica substrates, and the like.

DESCRIPTION OF SYMBOLS 1 ... Thin-film lithium secondary battery manufacturing apparatus, 2 ... Transfer chamber, 3 ... Transfer robot (substrate transfer mechanism), 4 ... Preparation taking-out chamber, 5 ... 1st sputtering chamber (collector layer formation chamber, protective layer formation chamber) ), 6 ... 2nd sputtering chamber (positive electrode layer forming chamber), 7 ... 3rd sputtering chamber (solid electrolyte layer forming chamber), 8 ... Negative electrode layer forming chamber, 9 ... Protective layer forming chamber, 10 ... Substrate, 11 DESCRIPTION OF SYMBOLS ... Substrate raising / lowering mechanism 46 ... Heater (substrate heating means) 51-54 ... 1st-4th target, 61 ... Target for positive electrode layer formation, 71 ... Target for solid electrolyte layer formation, 81 ... Evaporation source 91, 92... Evaporation source for raw material monomer

Claims (8)

A thin film lithium secondary battery manufacturing apparatus for manufacturing a thin film lithium secondary battery having a positive electrode layer, a negative electrode layer, a solid electrolyte layer, a positive electrode current collector layer, a negative electrode current collector layer, and a protective layer on a substrate in a vacuum. There,
A loading / unloading chamber for loading and unloading the substrate, a positive electrode layer forming chamber for forming a positive electrode layer containing lithium in the molecule on the substrate by sputtering, and forming a negative electrode layer on the substrate by vacuum deposition. A negative electrode layer forming chamber, a solid electrolyte layer forming chamber for forming a solid electrolyte layer containing lithium in the molecule on the substrate by sputtering, and a collector for forming a positive electrode current collecting layer and a negative electrode current collecting layer on the substrate by sputtering. An electric body layer forming chamber and a protective layer forming chamber for forming a protective layer on the substrate are respectively arranged around a transfer chamber having a substrate transfer mechanism and connected to the transfer chamber,
An apparatus for manufacturing a thin film lithium secondary battery, wherein a substrate heating means for annealing the positive electrode layer formed on the substrate is provided in the charging / unloading chamber.   The thin-film lithium secondary battery manufacturing apparatus according to claim 1, wherein the negative electrode layer forming chamber is provided with a substrate reversing mechanism for reversing the vertical relationship of the substrates in a vacuum.   The thin film lithium secondary battery manufacturing apparatus according to claim 1, wherein the current collector layer forming chamber is provided with a mask exchange mechanism for exchanging a film forming mask. A method of manufacturing a thin film lithium secondary battery using the thin film lithium secondary battery manufacturing apparatus according to any one of claims 1 to 3,
A plurality of targets including a current collector layer forming target and a protective layer forming target are disposed in the current collector layer forming chamber,
A step of carrying the substrate carried in from the charging / unloading chamber into the current collector layer forming chamber via the transfer chamber and forming the positive electrode current collecting layer on the substrate by sputtering;
Carrying the substrate into the charging / unloading chamber through the transfer chamber and annealing the positive electrode current collecting layer on the substrate;
Carrying the substrate into the positive electrode layer forming chamber through the transfer chamber and forming the positive electrode layer on the substrate by sputtering;
Carrying the substrate into the solid electrolyte layer forming chamber through the transfer chamber and forming the solid electrolyte layer on the substrate by sputtering;
Carrying the substrate into the negative electrode layer forming chamber through the transfer chamber and forming the negative electrode layer on the substrate by vacuum deposition;
Carrying the substrate into the current collector layer forming chamber through the transfer chamber and forming the negative electrode current collecting layer on the substrate by sputtering;
Carrying the substrate into the protective layer forming chamber via the transfer chamber and forming a first protective layer on the substrate by vapor deposition polymerization;
Carrying the substrate into the current collector layer forming chamber through the transfer chamber and forming a second protective layer on the first protective layer on the substrate by sputtering to form a thin film lithium secondary Battery manufacturing method.   The method for producing a thin film lithium secondary battery according to claim 4, further comprising a step of inverting the vertical relation of the substrate by the substrate inverting mechanism when forming the negative electrode layer.   6. The method according to claim 4, further comprising a step of exchanging the film-forming mask by the mask exchanging mechanism when forming the positive electrode current collecting layer, the negative electrode current collecting layer, and the second protective layer. The manufacturing method of the thin film lithium secondary battery of description.   The method of manufacturing a thin film lithium secondary battery according to claim 4, wherein the positive electrode layer is made of lithium cobalt oxide.   The method for producing a thin film lithium secondary battery according to claim 4, wherein the solid electrolyte layer is made of lithium phosphate oxynitride.

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