JP2012038433A - Thin-film solid secondary battery and method of manufacturing thin-film solid secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin-film solid secondary battery that is good in yield, and a method of manufacturing the thin-film solid secondary battery.SOLUTION: A thin-film solid secondary battery 10 includes a lower electrode active material 11a which comes into surface contact with a solid electrolyte 12, a lower electrode collector 11b which comes into surface contact with the lower electrode active material 11a, a terminal part 11c comprising an exposed surface electrically connecting with the lower electrode collector 11b and extended to a position where it does not come into surface contact with the lower electrode active material 11a to be exposed, or an exposed surface formed by exposing at least a part of the lower electrode collector 11b, an upper electrode active material 13a which comes into surface contact with the solid electrolyte 12, and an upper electrode collector 13b which comes into surface contact with the upper electrode active material 13a. The lower electrode active material 11a, solid electrolyte 12, upper electrode active material 13a, and upper electrode collector 13b are laminated in substantially the same shape in plan view, and an outer periphery of a contact surface between the lower electrode collector 11b and lower electrode active material 11a is formed inside an outer periphery of a lower surface of the lower electrode active material 11a.

Description

  The present invention relates to a thin film solid secondary battery and a method for manufacturing a thin film solid secondary battery, and more particularly, to simplify a manufacturing process using a mask, and to provide a thin film solid secondary battery and a thin film solid secondary battery with high yield. It relates to a manufacturing method.

  Small portable devices such as IC cards and mobile phones are widely used, and are becoming smaller, lighter and more multifunctional. Accordingly, batteries required for driving these devices are also required to be smaller and have higher energy density. Lithium ion secondary batteries have a higher energy density than other batteries and can be used in a wide range of applications, and are currently most widely used.

In addition to small portable devices, small and high energy density batteries are required for various small devices such as medical devices, sensor devices, and small functional robots.
However, with respect to miniaturization and thinning of the battery, conventional batteries using an electrolytic solution have limitations due to the thickness of the container. On the other hand, an all-solid battery using a gel electrolyte or a solid electrolyte instead of a solution is known. For example, a thin-film solid secondary battery using a solid electrolyte (for example, see Patent Document 1) has been proposed. Yes.

  As described in Patent Document 1, a thin film solid secondary battery has a structure in which a negative electrode current collector thin film, a negative electrode active material thin film, a solid electrolyte thin film, a positive electrode active material thin film, and a positive electrode current collector thin film are sequentially laminated on a substrate. A configuration or a configuration in which the above layers are stacked in the reverse order on a substrate. With such a configuration, the thin-film solid secondary battery can be made as thin as about 1 μm except for the substrate. Further, if the thickness of the substrate is reduced or a thin solid electrolyte film is used instead of the substrate, the overall thickness can be reduced and the size can be reduced. Furthermore, since it is an all-solid-state thin film solid secondary battery, it can be provided with high safety without inconvenience such as liquid leakage.

  Regarding the manufacturing technology of a thin film solid secondary battery, when laminating each layer of a thin film solid secondary battery (for example, a thin film solid lithium secondary battery), the material and the film forming technique are applied by a dry process such as a sputtering technique and a vacuum deposition technique. Various materials and techniques have been proposed. Among them, the film formation technology by sputtering is not only capable of forming a film with various targets in accordance with recent technological advances, but also downsizing the apparatus, simplifying the film formation process, and the costs associated therewith. This is a technology that is very important in the manufacturing technology of thin film solid state secondary batteries because it can be down.

  As a method for controlling the film formation area in the sputtering technique, a method is generally used in which a mask is attached to a substrate, the substrate film formation surface side is partially covered, and the film is formed only on the opening portion of the mask. Basically, in the film formation of the five layers constituting the thin film solid state secondary battery, it is necessary to exchange the mask for each lamination process in order to form each film in an arbitrary two-dimensional shape. However, when this mask is replaced, a slight “deviation” occurs due to technical problems. Along with this “deviation”, the positive electrode film (positive electrode current collector layer and positive electrode active material layer) and negative electrode film (negative electrode current collector). The body layer and the negative electrode active material layer) are in contact with each other at the end of the film, causing a short circuit. Therefore, despite the fact that a high-performance thin-film solid lithium secondary battery can be manufactured by the sputtering technique, there is a disadvantage that defective products are generated due to the above-described problems, and the yield is poor.

On the other hand, in Patent Document 2, in order to prevent a short circuit between the positive electrode film and the negative electrode film, the film formation area of each layer constituting the battery is sequentially reduced from the substrate side so that the layers do not overlap each other on a plane. A thin film solid secondary battery is disclosed.
Patent Document 3 discloses a thin-film solid-state secondary battery in which each layer is laminated on a foil and only the uppermost negative electrode active material layer is formed to have a smaller area than other layers. ing.

  As in the configurations disclosed in Patent Documents 2 and 3, by forming the area of the upper layer smaller than the lower layer, the upper layer is formed below. The occurrence of a short circuit can be suppressed without contact with each other at the periphery of the layer.

In Patent Document 4, a thin-film solid secondary in which a negative electrode active material layer having a small area is formed on a current collector layer, and an electrolyte layer having a large area is laminated so as to cover the periphery of the negative electrode active material layer. A battery is disclosed. Further, a positive electrode active material layer having a small area is formed on the electrolyte layer, and a current collector layer having a large area is formed on the positive electrode active material layer, thereby covering the periphery of the positive electrode active material layer. Also disclosed.
With such a configuration, the negative electrode active material layer, the positive electrode active material layer, and the current collector layer do not come into contact with each other.

Japanese Patent No. 3531866 Japanese Patent No. 3116857 International Publication No. 2007/102433 JP 2008-112635 A

  As described in Patent Documents 2 and 3, for each layer constituting the thin-film solid state secondary battery, the area of the layer stacked above is formed smaller than the area stacked below, or as disclosed in Patent Document 4 When the area of the layer formed over the material layer is increased to cover the periphery of the active material layer, the layers do not contact each other at the periphery, and as a result, a short circuit can be prevented.

  As described above, when a thin film solid-state secondary battery including each layer having a different area is formed by sputtering, it is necessary to replace the mask in order to form each layer having a different area. When replacing the mask, the inside of the sputtering apparatus needs to be once opened to the atmosphere. Therefore, when the mask is replaced, the surface of each layer is exposed to the atmosphere, so that the surface of each layer is oxidized and altered by moisture. As a result, battery performance (for example, battery life) may be reduced.

  Therefore, the techniques disclosed in Patent Documents 2 to 4 have a problem that the performance of the battery is deteriorated due to the large number of mask replacements, and the yield is lowered in the manufacture of the thin film solid secondary battery. Furthermore, if the mask is replaced for each layer, there is a problem that the manufacturing process becomes complicated and costs increase.

An object of the present invention is to reduce a short circuit occurring between upper and lower electrodes of a thin film solid secondary battery, and to provide a thin film solid secondary battery having a high yield and a method for manufacturing the thin film solid secondary battery.
Another object of the present invention is to simplify the manufacturing process by reducing the number of mask exchanges in the formation of each layer constituting a thin film solid secondary battery, and to provide a thin film solid secondary battery and a thin film with good battery performance. It is providing the manufacturing method of a solid secondary battery.

  According to the thin-film solid secondary battery of the present invention, the subject is a thin-film solid secondary in which a positive electrode of either positive or negative polarity, a solid electrolyte, and an upper electrode of the other polarity are formed in this order. The lower electrode includes a lower electrode active material that is in surface contact with the lower surface of the solid electrolyte, a lower electrode current collector that is in surface contact with the lower surface of the lower electrode active material, and the lower electrode current collector, An exposed surface extending and exposed to a position not conducting surface contact with the lower electrode active material, or an exposed surface from which at least a part of the lower electrode current collector is exposed, and the upper electrode comprises: An upper electrode active material in surface contact with the upper surface of the solid electrolyte, and an upper electrode current collector in surface contact with the upper surface of the upper electrode active material, the lower electrode active material, the solid electrolyte, and the upper electrode Electrode active material and upper electrode current collector Are laminated in substantially the same shape in plan view, and the outer periphery of the contact surface between the lower electrode current collector and the lower electrode active material is formed inside the outer periphery of the lower surface of the lower electrode active material. It is solved by.

Thus, in the thin film solid secondary battery of the present invention, the outer periphery of the contact surface between the lower electrode current collector and the lower electrode active material disposed above the lower electrode active material is more than the outer periphery of the lower surface of the lower electrode active material. It is formed inside. That is, with this configuration, the lower electrode current collector is not brought into contact with the upper electrode current collector by covering the end portion of the lower electrode current collector with the lower electrode active material disposed above the lower electrode current collector. Therefore, it is possible to provide a thin film solid-state secondary battery that not only can reliably prevent a short circuit but also has a high yield.
Then, the lower electrode current collector, the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector constituting the thin film solid secondary battery use a mask in a vacuum film forming apparatus on the substrate. However, since the structure from the lower electrode active material to the upper electrode current collector is substantially the same shape in plan view, all these layers are formed using the same mask. can do. In general, if each layer has a different shape, it is necessary to replace the mask. When the mask is replaced, the atmosphere in the vacuum film forming apparatus is released, and as a result, the thin film may be contaminated. On the other hand, since the thin-film solid state secondary battery of the present invention has substantially the same shape in plan view, it is possible to form a film from the lower electrode active material to the upper electrode current collector in a lump without replacing the mask when forming each layer. Thus, contamination of each layer due to mask replacement can be prevented. As a result, a thin film solid secondary battery with good battery performance can be obtained.
Furthermore, the thin film solid secondary battery of the present invention does not require mask exchange after the lower electrode active material is formed by the above-described configuration. Therefore, the thin-film solid secondary battery of the present invention needs to be opened to the atmosphere in the vacuum film-forming apparatus when forming an active material containing lithium, which is particularly related to battery performance, particularly when the lower electrode is a positive electrode. As a result, since the active material is not contaminated, a thin film solid secondary battery having good battery performance can be obtained.

At this time, it is preferable that the lower electrode current collector and the terminal portion are conductor film patterns formed on a thin plate-like insulating substrate having flexibility.
Thus, by using a thin plate-like insulating substrate including a film or the like, the thin film solid secondary battery of the present invention can be a thin film solid secondary battery having flexibility. Therefore, the electronic device on which the thin film solid secondary battery is mounted can be mounted on various electronic devices without limiting the installation location and the installation form. Furthermore, since a thin plate-like or film-like thin film solid secondary battery is lightweight, transportation costs can be reduced.

Moreover, it is preferable that the said terminal part is extended in the outer peripheral direction outer side of the said lower electrode electrical power collector.
Thus, by extending outward in the outer peripheral direction of the lower electrode current collector, the terminal portion is formed on the same side as the side on which the lower electrode current collector is laminated on the substrate. As a result, since various cables used for external connection are connected to this terminal part and the upper electrode current collector, a thin-film solid secondary battery having positive and negative terminals on the same surface is used. Can do. Therefore, when the thin-film solid secondary battery is mounted on an electronic device or the like, the wiring is simplified.

Furthermore, the lower electrode current collector is made of a conductive substrate, and an insulating film having an opening is formed on the conductive substrate, and an outer periphery of the opening of the insulating film is formed by the lower electrode active material. The structure formed inside the outer periphery of may be sufficient.
Thus, by using a conductive substrate, the conductive substrate can function as a lower electrode current collector. As a result, the configuration is simplified compared to the case where an insulating substrate is used. Further, since the step of separately forming the lower electrode current collector by film formation can be omitted, the manufacturing process of the thin film solid secondary battery can be simplified.

At this time, the lower electrode active material is made of a material containing lithium, and the solid electrolyte includes lithium phosphate (Li ₃ PO ₄ ), lithium phosphate oxynitride in which oxygen of lithium phosphate is partially substituted with nitrogen ( LiPON) or a transition metal and a composite oxide containing Li and N is preferable.
Thus, using a material containing lithium as the lower electrode active material as the lower electrode active material and further containing these compounds with good lithium ion conductivity in the solid electrolyte, it has good charge / discharge characteristics. A thin film solid lithium ion secondary battery can be provided.

  According to the method for manufacturing a thin-film solid secondary battery according to the present invention, the subject is a lower electrode current collector, a terminal portion and a lower electrode active material that constitute a lower electrode of either positive or negative polarity, a solid electrolyte, A method of manufacturing a thin-film solid secondary battery in which an upper electrode active material and an upper electrode current collector constituting an upper electrode of the other polarity are formed in this order, wherein the lower electrode current collector is formed on an insulating substrate Forming a conductor film pattern that constitutes the terminal portion that is electrically connected to the body and the lower electrode current collector and is exposed at least partially, and a frame-like mask that defines the thin film formation region, The side on which the conductor film pattern on the insulating substrate is formed at a position where the outer periphery is outside the outer periphery of the lower electrode current collector and a part of the terminal portion is not included in the thin film formation region And the step of arranging the mass Forming the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector in this order in the thin film formation region. That is solved.

At this time, the layers of the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector are formed in substantially the same shape in plan view, and these layers are continuously formed without mask replacement. As a result, it is possible to omit the opening of the atmosphere in the vacuum film forming apparatus and the exhaust of the vacuum film forming apparatus when the mask is replaced. As a result, the battery cell production time is greatly shortened and the manufacturing cost is reduced. Can do.
In addition, by performing continuous film formation without exchanging the mask, work in the air can be reduced, so that it is possible to prevent deterioration of the thin film constituting the battery cell. Furthermore, even when a plurality of persons in charge are involved in the manufacturing process, it is possible to reduce the possibility of a difference in battery performance depending on the difference in work efficiency between persons in charge. Therefore, the yield is improved and a thin film solid secondary battery with uniform quality can be manufactured.
Furthermore, the lower electrode current collector and the upper electrode current collector formed on the insulating substrate are unlikely to come into contact with each other, and as a result, a thin film solid secondary battery having a high short-circuit prevention effect can be manufactured.

  In addition, according to the method of manufacturing a thin film solid secondary battery according to the present invention, the problem is that the lower electrode current collector, the terminal portion and the lower electrode active material constituting the lower electrode of either positive or negative polarity, and the solid A method of manufacturing a thin-film solid secondary battery in which an electrolyte, an upper electrode active material constituting an upper electrode of the other polarity, and an upper electrode current collector are formed in this order, and the lower electrode current collector is constituted Forming an insulating film having an opening on the surface of the conductive substrate and a frame-shaped mask for partitioning the thin film formation region, the outer periphery of the thin film formation region is outside the outer periphery of the opening A position on the conductive substrate on the side where the insulating film is formed, and in the thin film formation region of the mask, the lower electrode active material, the solid electrolyte, and the upper electrode active Material and the upper electrode current collector in succession. Be provided with a step of forming a film on, it is solved by.

At this time, each layer of the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector can be continuously formed without mask replacement. This eliminates the need for opening the atmosphere to replace the mask and eliminates the time required for evacuating the vacuum film forming apparatus. As a result, the battery cell manufacturing time can be shortened and the manufacturing cost can be reduced. Can do.
In addition, when a conductive substrate is used, an insulating film having an opening on the surface thereof is formed, so that a lower electrode current collector constituted by the conductive substrate and an upper electrode current collector formed thereabove are formed. As a result, it is possible to manufacture a thin-film solid secondary battery that is less likely to come into contact with the body and has a high short-circuit prevention effect. At this time, by using a conductive substrate functioning as a lower electrode current collector, it is not necessary to form a separate film for the lower electrode current collector, so that the manufacturing process can be simplified.

At this time, the lower electrode active material is made of a material containing lithium, and the solid electrolyte is lithium phosphate (Li ₃ PO ₄ ), lithium phosphate oxynitride in which oxygen of lithium phosphate is partially substituted with nitrogen (LiPON) or any one selected from a transition metal and a composite oxide containing Li and N is preferable.
As described above, when the lower electrode active material is formed, a film containing a lithium-containing material is formed, and further, a solid electrolyte is formed using these compounds having good lithium ion conductivity. A thin film solid lithium ion secondary battery having charge / discharge characteristics can be manufactured.

According to the thin film solid secondary battery of the present invention, the outer periphery of the contact surface between the lower electrode current collector and the lower electrode active material is formed on the inner side of the outer periphery of the lower surface of the lower electrode active material. A short circuit due to contact between the current collectors of the electrode and the upper electrode can be effectively prevented, and as a result, a thin film solid secondary battery with a high yield can be provided. Furthermore, each layer of the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector has substantially the same shape in plan view, so that it can be continuously formed without replacing the mask, and the battery efficiency is improved. In particular, it is possible to form a film without contaminating the affected active material layer, and the battery performance of the thin film solid secondary battery is improved.
In addition, according to the method for manufacturing a thin film solid secondary battery of the present invention, each layer disposed upward from the lower electrode active material can be continuously formed without mask replacement, thereby simplifying the manufacturing process. The manufacturing time can be greatly shortened, and the costs associated with the manufacture of the thin film solid secondary battery can be reduced.

1 is a schematic perspective view of a thin-film solid secondary battery according to Embodiment 1 of the present invention. It is a top view of the thin film solid secondary battery which concerns on Embodiment 1 of this invention. It is a schematic sectional drawing equivalent to the AA line of FIG. It is a top view of the thin film solid secondary battery which concerns on embodiment of a comparative example. It is a schematic sectional drawing of the thin film solid secondary battery which concerns on embodiment of a comparative example. It is a graph of the discharge curve of the thin film solid secondary battery which concerns on the Example and comparative example of this invention. It is a schematic perspective view of the thin film solid secondary battery which concerns on Embodiment 2 of this invention. It is a top view of the thin film solid secondary battery which concerns on Embodiment 2 of this invention. It is a schematic sectional drawing equivalent to the BB line of FIG. It is a schematic sectional drawing of the thin film solid secondary battery which concerns on Embodiment 3 of this invention. It is a schematic sectional drawing of the thin film solid secondary battery which concerns on Embodiment 4 of this invention. It is a schematic sectional drawing of the thin film solid secondary battery which concerns on Embodiment 5 of this invention. It is a schematic sectional drawing of the thin film solid secondary battery which concerns on Embodiment 6 of this invention. It is a top view of the thin film solid secondary battery which concerns on Embodiment 7 of this invention.

  A thin film solid secondary battery and a method for manufacturing a thin film solid secondary battery according to an embodiment of the present invention will be described with reference to the drawings. The materials, arrangements, configurations, and the like described below do not limit the present invention and can be variously modified within the scope of the gist of the present invention.

  1 to 3 relate to Embodiment 1 of the present invention. FIG. 1 is a schematic perspective view of a thin film solid secondary battery, FIG. 2 is a plan view of the thin film solid secondary battery, and FIG. 4 and 5 relate to a comparative example, FIG. 4 is a plan view of a thin film solid secondary battery, FIG. 5 is a schematic cross sectional view of a thin film solid secondary battery, FIG. 6 is a graph of discharge curves of thin film solid state secondary batteries according to examples and comparative examples of the present invention. FIGS. 7 to 9 relate to Embodiment 2 of the present invention, and FIG. 7 is a thin film solid state secondary battery. 8 is a schematic perspective view of the battery, FIG. 8 is a plan view of the thin-film solid secondary battery, FIG. 9 is a schematic cross-sectional view corresponding to the line BB of FIG. 7, and FIG. 10 is a thin-film solid according to Embodiment 3 of the present invention. FIG. 11 is a schematic sectional view of a secondary battery, FIG. 11 is a schematic sectional view of a thin film solid secondary battery according to Embodiment 4 of the present invention, and FIG. 12 is an embodiment of the present invention. FIG. 13 is a schematic sectional view of a thin film solid secondary battery according to Embodiment 6 of the present invention, and FIG. 14 is a thin film according to Embodiment 7 of the present invention. It is a top view of a solid secondary battery. In addition, each layer which comprises a thin film solid secondary battery is drawn with emphasis on thickness rather than actuality for description.

[Embodiment 1]
As shown in FIGS. 1 and 3, the thin-film solid secondary battery 10 according to Embodiment 1 of the present invention includes a lower electrode 11 having either positive or negative polarity, a solid electrolyte layer 12, and an upper electrode having the other polarity. 13 are formed in this order. The lower electrode 11, the solid electrolyte layer 12, and the upper electrode 13 are sequentially stacked on the insulating substrate S. The lower electrode 11 includes a lower electrode active material layer 11a, a lower electrode current collector layer 11b, and a first terminal. The upper electrode 13 includes an upper electrode active material layer 13a and an upper electrode current collector layer 13b.
In the first embodiment, the lower electrode active material layer 11a is the “lower electrode active material” in the claims, the lower electrode current collector layer 11b is the “lower electrode current collector” in the claims, the upper electrode The active material layer 13a corresponds to the “upper electrode active material” in the claims, and the upper electrode current collector layer 13b corresponds to the “upper electrode current collector” in the claims.

  The lower electrode 11 is formed by laminating a lower electrode current collector layer 11b and a lower electrode active material layer 11a in order from the top of the insulating substrate S. The lower electrode 11 extends to a position where the lower electrode active material layer 11a is not in contact with the first terminal portion 11c including the exposed exposed surface, that is, the outer side in the outer peripheral direction of the lower electrode current collector layer 11b. The first terminal portion 11c having a substantially rectangular shape is provided. (In FIGS. 2 and 3, for the sake of explanation, the lower electrode current collector layer 11b and the first terminal portion 11c are drawn separated by a dotted line, but they are actually formed in a continuous thin film shape. The first terminal portion 11c is formed so as to be connected to various cables for external connection, etc., and is electrically connected to the lower electrode current collector layer 11b and partially exposed. . In the first embodiment, the first terminal portion 11c corresponds to a “terminal portion” in the claims, and is connected to a cable for external connection.

  A known technique is used to connect the first terminal portion 11c and various cables, for example, by heating and thermocompression bonding with an anisotropic conductor (ACF) and a flexible flat cable stacked in this order. Connected. In addition, it may connect not only using ACF but other connection methods, such as a solder connection, and may use a metal conducting wire instead of a flexible flat cable. When using a metal lead, the connection method can be wire bonding, solder, laser welding, or the like.

  On the other hand, as shown in FIG. 3, the upper surface of the lower electrode active material layer 11 a is formed so as to be in surface contact with the lower surface (bottom surface) of the solid electrolyte layer 12 formed on the lower electrode 11. The lower surface of the lower electrode active material layer 11a is formed so as to be in surface contact with the upper surface of the lower electrode current collector layer 11b.

  The lower electrode active material layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b are laminated in substantially the same shape in plan view (substantially rectangular in the first embodiment). ing. Therefore, it is not necessary to replace the mask when forming the lower electrode active material layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b. When the mask is exchanged, the vacuum film forming apparatus is opened to the atmosphere. However, since the same mask can be used for film formation from the lower electrode active material layer 11a to the upper electrode current collector layer 13b, the lower electrode active material is used. The thin film solid secondary battery 10 with good battery performance can be provided without the influence from the atmosphere being released from the layer 11a to the upper electrode current collector layer 13b.

  The mask used for forming the film from the lower electrode active material layer 11a to the upper electrode current collector 13b may be a substantially rectangular shape as shown in FIGS. 1 and 2, or other shapes. good. Further, in the first embodiment, for connection with various cables, the first electrode is formed from each of the substantially rectangular lower electrode active material layer 11a, solid electrolyte layer 12, upper electrode active material layer 13a, and upper electrode current collector layer 13b. The two terminal portions 14 are formed to protrude in the same shape. (In FIG. 2, for the sake of explanation, the upper electrode current collector layer 13b and the second terminal portion 14 are drawn separated by a dotted line, but they are actually formed as a continuous thin film.) The second terminal portion 14 is preferably formed at a position symmetrical to the first terminal portion 11c. Since various cables can be directly connected to the upper electrode current collector layer 13b by the above method, the second terminal portion 14 protrudes from the upper electrode current collector layer 13b as in the first embodiment. It does not have to be extended.

  The contact surface between the lower electrode current collector layer 11b and the lower electrode active material layer 11a, that is, the outer periphery of the upper surface of the lower electrode current collector layer 11b is formed inside the outer periphery of the lower electrode active material layer 11a. ing. As shown in FIG. 2, in the thin-film solid secondary battery 10 of Embodiment 1, the outer periphery of the lower electrode current collector layer 11 b is formed in a substantially rectangular shape, and the first outward from the outer periphery toward the outer side. A terminal portion 11c is extended.

  The lower electrode current collector layer 11b is formed to have a smaller area than the lower electrode active material layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b. The upper surface of the lower electrode current collector layer 11b is encompassed by the lower electrode active material layer 11a. That is, the lower electrode current collector layer 11b is entirely covered with the lower electrode active material layer 11a, and further, the outer peripheral end portion thereof is another layer (solid electrolyte layer 12, upper electrode active material layer 13a, upper The electrode current collector layer 13b) is disposed so as not to contact the electrode current collector layer 13b). Therefore, the outer peripheral end of the lower electrode current collector layer 11b (more specifically, the contact surface between the lower electrode current collector layer 11b and the lower electrode active material layer 11a) is at least the outer peripheral end of the lower electrode active material layer 11a. It is the structure arrange | positioned inside with respect to (refer FIG. 3).

  As described above, when the outer peripheral end portion of the lower electrode current collector layer 11b is at least inside the outer peripheral end portion of the lower electrode active material layer 11a, the lower electrode current collector layer 11b becomes lower electrode active material. Since the shape is completely covered by the layer 11a, the lower electrode current collector layer 11b does not come into contact with the layer formed above the solid electrolyte layer 12. Therefore, a short circuit can be prevented, and as a result, the thin film solid secondary battery 10 with a high yield can be obtained.

  On the other hand, the first terminal portion 11c extending from the lower electrode current collector layer 11b is formed so that at least a part thereof is exposed, and as shown in FIG. The layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b are formed on the inner side of the outer periphery, but a part of the lower electrode active material layer 11a and the solid electrolyte are formed. The layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b are extended to the outside of the outer periphery. As described above, the first terminal portion 11c extending from the lower electrode current collector layer 11b is provided, and each of the first terminal portions 11c formed above the lower electrode current collector layer 11b ( The thin-film solid secondary battery of the present invention includes an exposed portion that is not laminated with the lower electrode active material layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b). 10 can be easily connected to various cables.

  A protective film (not shown) is provided to cover the exposed portion of the first terminal portion 11c and the portion other than the second terminal portion 14 of the thin-film solid secondary battery 10 having the above configuration. In addition, as described above, the second terminal portion 14 is not specially formed, and the protective film is not provided in part on the upper electrode current collector layer 13b, and various cables are connected to the part. It is also good.

  Hereinafter, a configuration of each layer will be described by taking a thin film solid lithium ion secondary battery using the lower electrode 11 as a positive electrode and the upper electrode 13 as a negative electrode as an example. Of course, the lower electrode 11 may be a negative electrode and the upper electrode 13 may be a positive electrode. However, as will be described later, in order to protect the surface of the positive electrode active material containing lithium, the lower electrode 11 is used as a positive electrode, and the solid electrolyte layer 12 and the upper electrode 13 serving as a negative electrode are stacked thereon. Further, lithium contained in the positive electrode active material can be prevented from moving to the negative electrode active material layer during film formation, and deterioration of battery characteristics can be suppressed.

As the insulating substrate S, glass, a resin substrate, or the like can be used. As the resin substrate, polyimide, PET, or the like can be used. In addition, as long as it can be handled without breakage, a thin plate-like film that is formed into a thin plate shape and has flexibility and can be bent can be used. Thus, while using the flexible insulating substrate S formed in a thin plate shape such as a film, each layer is constituted by a thin film of about several μm to several tens of μm, so that the battery as a whole is flexible. It is possible to provide a thin-film solid secondary battery 10 including
In addition, these insulating substrates S have additional characteristics such as increasing transparency, preventing diffusion of alkali elements such as Na, increasing heat resistance, and providing gas barrier properties. More preferred.

  The lower electrode current collector layer 11b and the first terminal portion 11c functioning as the positive electrode current collector layer are formed of a metal film having good adhesion to the insulating substrate S and having low electric resistance. For the lower electrode current collector layer 11b, a conductive film having good adhesion to the lower electrode active material layer 11a as the positive electrode active material layer and having a low electric resistance can be used.

In order for the first terminal portion 11c to function satisfactorily as an extraction electrode, the sheet resistance is desirably 1 kΩ / □ or less. When the film thickness of the first terminal portion 11c is set to 0.1 μm or more, the first terminal portion 11c needs to be formed of a substance having a resistivity of 1 × 10 ⁻² Ω · cm or less. As such a substance, for example, vanadium, titanium, niobium, aluminum, copper, nickel, gold or the like can be used. With these materials, the first terminal portion 11c can be formed to a thickness of about 0.05 to 1 μm, which is as thin as possible and has a low electrical resistance.

  The lower electrode current collector layer 11b can use vanadium, titanium, niobium, aluminum, copper, nickel, gold, or the like, as in the first terminal portion 11c. When the lower electrode current collector layer 11b and the first terminal portion 11c are formed using the same material and the same mask, the manufacturing process of the battery cell can be simplified, which is preferable.

The lower electrode active material layer 11a functioning as the positive electrode active material layer is not particularly limited as long as it contains lithium and can release and occlude lithium ions. Preferably, manganese, which is a transition metal, It is preferable to use a metal oxide thin film containing at least one of cobalt and nickel and lithium. For example, lithium-manganese oxide (LiMn ₂ O ₄ , Li ₂ Mn ₂ O _4, etc.), lithium-cobalt oxide (LiCoO ₂ , LiCo ₂ O _4, etc.), lithium-nickel oxide (LiNiO ₂ , LiNi ₂ O, etc.) ₄ ), lithium-manganese-cobalt oxide (LiMnCoO ₄ , Li ₂ MnCoO ₄ etc.), lithium-titanium oxide (Li ₄ Ti ₅ O ₁₂ , LiTi ₂ O ₄ etc.), etc. can be used. The film thickness of the lower electrode active material layer 11a is desirably as thin as possible, but is preferably about 0.05 to 5 μm that can secure charge / discharge capacity.

The solid electrolyte layer 12 is composed of lithium phosphate (Li ₃ PO ₄ ) having good lithium ion conductivity, lithium phosphate oxynitride glass (LiPON) in which oxygen of the lithium phosphate is partially substituted with nitrogen, or Ta and Nb. Any one or more transition metals and composite oxides containing Li and N can be used. The thickness of the solid electrolyte layer 12 is preferably about 0.05 to 1 [mu] m, where generation of pinholes is reduced and as thin as possible.

The upper electrode active material layer 13a functioning as the negative electrode active material layer is not particularly limited as long as it is a material capable of detaching and occluding lithium ions, and is preferably a silicon-manganese alloy (Si-Mn), silicon - cobalt alloy (Si-Co), silicon - nickel alloy (Si-Ni), lithium - titanium oxide _{(LiTi 2 O 4, Li 4} Ti 5 O 12 , etc.), niobium pentoxide _{(Nb 2 O} 5), Titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), nickel oxide (NiO), tin-added indium oxide (ITO), aluminum added Zinc oxide (AZO), gallium-added zinc oxide (GZO), antimony-added tin oxide (ATO), fluorine-added acid Tin (FTO), it is preferable to use such nickel oxide lithium is added (NiO-Li).

The upper electrode current collector layer 13b functioning as the negative electrode current collector layer can be formed using a conductive film having good adhesion to the upper electrode active material layer 13a as the negative electrode active material layer and having low electric resistance.
Vanadium, titanium, niobium, aluminum, copper, nickel, gold, or the like can be used similarly to the lower electrode current collector layer 11b and the first terminal portion 11c.

Also, when niobium oxide (Nb ₂ O ₅ ) is used as the negative electrode active material, the negative electrode current collector is niobium, so that the oxygen gas flow rate during sputtering film formation is adjusted using the same niobium metal target. Can be produced. Thereby, when manufacturing a battery cell, the number of required targets and the number of power supplies can be reduced, the apparatus can be reduced in size, and the cost can be reduced.

When the thin-film solid secondary battery 10 is charged, lithium is released as ions from the lower electrode active material layer 11a serving as the positive electrode active material layer, and the thin film solid secondary battery 10 serves as the negative electrode active material layer via the solid electrolyte layer 12. The upper electrode active material layer 13a is occluded. At this time, electrons are emitted from the lower electrode active material layer 11a as the positive electrode active material layer to the outside.
Further, during discharge, lithium is released as ions from the upper electrode active material layer 13a serving as the negative electrode active material layer, and is inserted into the lower electrode active material layer 11a serving as the positive electrode active material layer via the solid electrolyte layer 12. . At this time, electrons are emitted from the upper electrode active material layer 13a as the negative electrode active material layer to the outside.

  Conventionally, an active material layer containing lithium related to the transfer of electrons is formed by forming a positive electrode and a negative electrode active material layer to have a smaller area than other layers and covering the active material layer. Is protected and battery performance can be improved. However, in order to form the upper layer so as to completely cover the active material layer, it is necessary to replace the mask. At the time of replacing the mask, the thin-film solid lithium ion secondary battery being manufactured is exposed to the atmosphere and contaminated. There is a high probability that battery performance may be reduced as a result.

  On the other hand, after forming the lower electrode current collector layer 11b containing lithium related to the exchange of electrons, the mask is exchanged, and each film above the lower electrode active material layer 11a is replaced with the lower electrode current collector layer. The lower electrode active material layer 11a is not contaminated by using the same mask so as to be a layer having a larger area than 11b and continuously forming a vacuum state. As a result, the thin film solid secondary battery 10 with good battery performance can be provided.

  Next, a manufacturing method for the thin-film solid secondary battery 10 according to Embodiment 1 of the present invention will be specifically described. The manufacturing method of the thin film solid secondary battery 10 of the present invention includes a lower electrode current collector layer 11b, a first terminal portion 11c and a lower electrode active material 11a constituting a lower electrode 11 of either positive or negative polarity, A method for manufacturing a thin-film solid secondary battery 10 in which an electrolyte layer 12 and an upper electrode active material layer 13a and an upper electrode current collector layer 13b constituting an upper electrode 13 of the other polarity are formed in this order, Conductive film pattern forming step of forming a conductive film pattern (lower electrode current collector layer 11b and first terminal portion 11c) with a conductive conductive film using a mask on insulating substrate S, and forming a thin film The frame-shaped mask that divides the region is a position where the outer periphery of the thin film forming region is outside the outer periphery of the lower electrode current collector layer 11b and a part of the first terminal portion 11c is not included in the thin film forming region. Insulating group A mask exchange step disposed on the side on which the conductor film pattern on S is formed, and a lower electrode active material layer 11a, a solid electrolyte layer 12, and an upper electrode active material layer 13a in the thin film formation region of the mask after the exchange. And a film forming step for successively forming the upper electrode current collector layer 13b in this order. Hereinafter, each step will be described in detail.

(1. Conductive film pattern forming process)
In the method of manufacturing the thin film solid secondary battery 10 of the present invention, first, an island-shaped conductor film in which the lower electrode current collector layer 11b and the first terminal portion 11c are continuously integrated on the insulating substrate S. Form a pattern. At this time, the target of the above-mentioned material constituting the lower electrode current collector layer 11b and the first terminal portion 11c is used, and the first electrode formed continuously to the lower electrode current collector layer 11b and the lower electrode current collector layer 11b. A film is formed by a sputtering method using a mask that partitions the shape of one terminal portion 11c. At this time, rather than forming an island-shaped conductor film pattern on one insulating substrate S, a large number of conductor film patterns are formed, and other layers are formed above each conductor film pattern. After the lamination, by dividing the insulating substrate S together, a large number of thin film solid secondary batteries 10 can be manufactured with a small number of film formations.

(2. Mask exchange process)
After performing the conductor film pattern forming step, the vacuum film forming apparatus is opened to the atmosphere, and the mask used to form the conductor film pattern including the lower electrode current collector layer 11b and the first terminal portion 11c is removed. . Thereafter, a frame-like mask in which the outer peripheral end portion of the thin film forming region is disposed outside the outer peripheral end portion of the lower electrode current collector layer 11b. At this time, on the insulating substrate S, a mask for partitioning the thin film formation region is disposed on the side where the lower electrode current collector layer 11b and the first terminal portion 11c are formed. In addition, since this mask forms the exposed part (namely, part which contacts various cables, a cable connection part) of the 1st terminal part 11c, on the 1st terminal part 11c, lower electrode collector layer 11b and It forms so that the edge part on the opposite side to a connection part may be covered (refer FIG. 2).

(3. Film formation process)
After performing the mask exchange step, the lower electrode active material layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b are identical until each layer has a predetermined thickness in this order. Films are continuously formed using a mask.

  It is generally known that a lithium-containing oxide that is a constituent material of a lithium secondary battery is easily deteriorated by moisture and oxidation. As a countermeasure, a dry room, a glove box, etc. are required. According to the present invention, the lower electrode active material layer 11a to the upper electrode current collector layer 13b constituting the battery cell are continuously produced in a vacuum film forming apparatus. Therefore, it is suitable as a method for manufacturing a lithium secondary battery.

  In addition, as a method for forming each layer from the lower electrode current collector layer 11b to the upper electrode current collector layer 13b, a vacuum film forming method such as a sputtering method, an electron beam vapor deposition method, a heat vapor deposition method, a coating method, or the like is used. be able to. It is preferable to use a vacuum film-forming method that can form a thin film more thinly and uniformly. More preferably, it is preferable to use a sputtering method in which there is little deviation in the atomic composition from the vapor deposition material and uniform film formation is possible.

  Thus, the mask is configured so that the outer periphery of each layer above the lower electrode active material layer 11a is outside the outer periphery of the lower electrode current collector layer 11b, and the layers after the lower electrode active material layer 11a are collectively As a result, the outer peripheral ends of the lower electrode current collector layer 11b and the upper electrode current collector layer 13b are spaced apart. Accordingly, it is possible to prevent a short circuit due to the lower electrode current collector layer 11b coming into contact with the upper electrode current collector layer 13b due to a “shift” of the mask or the like. Furthermore, after the lower electrode active material layer 11a is formed, it is not necessary to replace the mask before the formation of the solid electrolyte layer 12, so that the contamination of the lower electrode active material layer 11a can be prevented and the battery performance is improved. In addition, the manufacturing process can be simplified.

In the first embodiment, either the lower electrode current collector layer 11b or the upper electrode current collector layer 13b is a negative electrode current collector layer, the negative electrode current collector is niobium, and the lower electrode active material layer 11a. Alternatively, when any one of the upper electrode active material layers 13a is a negative electrode active material layer and the negative electrode active material is niobium oxide (Nb ₂ O ₅ ), a film can be formed by a DC sputtering method. Compared to the above, the film formation speed is improved, the film formation time can be shortened, the production efficiency is improved, and the manufacturing cost can be reduced.

  In the first embodiment, a thin film solid lithium ion secondary battery has been described as an example. However, it is considered that various thin film solid type secondary batteries having the above-described configuration can be manufactured. . Among them, a thin-film solid-state lithium secondary battery is considered to be suitable from the viewpoint of excellent battery characteristics such as energy density and relatively easy thinning of the constituent materials. .

Next, examples according to the first embodiment of the present invention and comparative examples for the same will be described with reference to the drawings.
(Example)
1 to FIG. 3, on the insulating substrate S, a lower electrode current collector layer 11b that is a positive electrode current collector layer, a lower electrode active material layer 11a that is a positive electrode active material layer, a solid electrolyte layer 12, The upper electrode active material layer 13a, which is a negative electrode active material layer, and the upper electrode current collector layer 13b, which is a negative electrode current collector layer, were formed in this order by sputtering, and the thin film solid secondary battery 10 was produced. At this time, as described above, after the first terminal portion 11c and the lower electrode current collector layer 11b are formed in advance on the insulating substrate S, the mask is exchanged with the air released, and then the lower electrode active material is formed. The layer 11a, the solid electrolyte layer 12, the upper electrode active material layer 13a, and the upper electrode current collector layer 13b were continuously formed.

As the insulating substrate S, borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm was used.
The lower electrode current collector layer 11b and the first terminal portion 11c were formed by a DC magnetron sputtering method using a titanium (Ti) target. At this time, the film was formed with a DC power of 1 KW and no heating. As a result, a titanium thin film having a thickness of 0.1 μm was formed as an island-shaped conductor film pattern in which the lower electrode current collector layer 11b and the first terminal portion 11c were integrally continuous.

The lower electrode active material layer 11a was formed by RF magnetron sputtering using a lithium manganate (LiMn ₂ O ₄ ) target and introducing oxygen. The film was formed with an RF power of 1 KW and no heating. Thereby, a LiMn ₂ O ₄ thin film having a thickness of 0.2 μm was formed.
Further, the solid electrolyte layer 12 was formed by RF magnetron sputtering using a sintered phosphor target of lithium phosphate (Li ₃ PO ₄ ) and introducing nitrogen. The film was formed with an RF power of 1 KW and no heating. Thereby, a lithium phosphate oxynitride glass (LiPON) thin film having a thickness of 0.1 μm was formed.

The upper electrode active material layer 13a was formed by DC magnetron sputtering using a niobium (Nb) target and introducing oxygen. The film was formed with a DC power of 1 KW and no heating. This formed a 0.1 μm niobium oxide (Nb ₂ O ₅ ) thin film.
The upper electrode current collector layer 13b was formed by a DC magnetron sputtering method using a titanium (Ti) target in the same manner as the lower electrode current collector layer 11b and the first terminal portion 11c. The film was formed with a DC power of 1 KW and no heating. Thereby, a titanium thin film having a thickness of 0.1 μm was formed.

(Comparative example)
A thin film solid secondary battery 100 according to an embodiment of a comparative example will be described with reference to the drawings.
FIG. 4 is a plan view of the thin-film solid secondary battery 100 according to the embodiment of the comparative example, and FIG. 5 is a schematic cross-sectional view of the thin-film solid secondary battery 100 according to the embodiment of the comparative example.

  The thin film solid state secondary battery 100 of the comparative example has a configuration in which the outer periphery of the lower electrode current collector layer 11b is formed inside the outer periphery of the lower electrode active material layer 11a, that is, the lower electrode current collector layer 11b is exposed. Unlike the thin-film solid secondary battery 10 of Embodiment 1 (see FIGS. 1 to 3) covered with the lower electrode active material layer 11a, the outer periphery of the lower electrode current collector layer 110b is lower It is characterized by being formed outside the outer periphery of each layer formed above the electrode active material layer 110a.

Hereinafter, the configuration of the thin film solid secondary battery 100 according to the embodiment of the comparative example will be described.
As shown in FIGS. 4 and 5, the thin-film solid secondary battery 100 according to the comparative example includes a first terminal part 110 c, a lower electrode current collector layer 110 b, a lower electrode active part on an insulating substrate S. The material layer 110a, the solid electrolyte layer 120, the upper electrode active material layer 130a, and the upper electrode current collector layer 130b are sequentially stacked.

  And from the outer periphery of the lower electrode collector layer 110b formed on the insulating substrate S, the first terminal portion 110c extends on the same plane, and the lower electrode collector layer 110b The area is wider than each layer. The lower electrode current collector layer 110b and the first terminal portion 110c are formed in a lump using a mask that partitions the thin film formation region, and then the mask is exchanged so that the lower electrode active material layer 110a, the solid electrolyte layer 120, The upper electrode active material layer 130a and the upper electrode current collector layer 130b are successively formed in this order using the same mask until each layer has a predetermined thickness. Note that the mask used at this time is formed such that the outer periphery of the thin film forming region partitioned is disposed on the inner side with respect to the outer periphery of the lower electrode current collector layer 110b.

  Therefore, as compared with the thin-film solid secondary battery 10 of Embodiment 1 described above, the thin-film solid secondary battery 100 of the comparative example has an outer peripheral position of the lower electrode current collector layer 110b, that is, the lower electrode active material layer 110a. The constituent materials and the respective manufacturing steps are the same except that the area ratio is different and the shape of the mask is different. Therefore, the description thereof is omitted.

  4 and 5, on the insulating substrate S, a lower electrode current collector layer 110b that is a positive electrode current collector layer, a lower electrode active material layer 110a that is a positive electrode active material layer, a solid electrolyte layer 120, The upper electrode active material layer 130a that is the negative electrode active material layer and the upper electrode current collector layer 130b that is the negative electrode current collector layer were formed in this order by the sputtering method, and the thin film solid secondary battery 100 was manufactured. In addition, compared with the Example of the said thin film solid secondary battery 10, through the same material and manufacturing process except the point that the mask shape for forming the layer above the lower electrode active material layer 110a differs, A thin film solid secondary battery 100 was produced.

  Table 1 summarizes the results of yield, energy efficiency (ratio of discharge current capacity to charge current capacity), etc., for the thin film solid secondary battery 10 and the thin film solid secondary battery 100 obtained as described above. The results of Examples and Comparative Examples are shown in Table 1 below.

Measurement is done with a charge / discharge meter.
Charging current = 0.06mA, charging end voltage = 3.5V
Discharge current = 0.06 mA, discharge end voltage = 0.3 V
The yield was calculated assuming that the battery operation was confirmed as a non-defective product.

As a result, the thin-film solid secondary battery 10 which is an example of the present invention was better than the thin-film solid secondary battery 100 of the comparative example in terms of yield and energy efficiency.
Regarding the yield, the thin-film solid secondary battery 10 of the example of the present invention was 100% (measured number 216, movable number 216), whereas the thin-film solid secondary battery 100 of the comparative example was 73.8%. (Measured number 648, movable number 478), indicating that the yield of the thin-film solid secondary battery 10 of the present invention is extremely high. Furthermore, regarding the energy efficiency, the thin-film solid secondary battery 10 of the present invention was 86.2%, whereas the thin-film solid secondary battery 100 of the comparative example was 43.0%. It was shown that the energy efficiency of the secondary battery 10 is extremely high. That is, it is shown that the thin film solid secondary battery 10 of the present invention has a very high discharge current capacity retention rate with respect to the charge current capacity.

  Further, the discharge characteristics of the thin film solid secondary battery 10 and the thin film solid secondary battery 100 were evaluated. The results of Examples and Comparative Examples are shown in FIG. The measurement was performed under the conditions described above.

  As a result, it was shown that the thin film solid secondary battery 10 which is an example of the present invention can maintain a higher battery voltage during discharging at the same battery capacity. For example, when comparing battery capacities that can maintain a battery voltage of 0.5 V or more, the thin film solid secondary battery 10 of the example has a battery capacity about 1.1 times that of the thin film solid secondary battery 100 of the comparative example. Yes.

  Therefore, according to the above comparison, the upper surface of the lower electrode current collector layer 11b is covered with the lower electrode active material layer 11a, and the layers stacked above the lower electrode active material layer 11a are collectively formed, so that the battery performance and It was shown that the yield was greatly improved.

  Furthermore, Embodiment 2 of the present invention will be described with reference to the drawings. 7 to 9 relate to Embodiment 2 of the present invention. FIG. 7 is a schematic perspective view of the thin film solid secondary battery 20, FIG. 8 is a plan view of the thin film solid secondary battery 20, and FIG. It is sectional drawing equivalent to a BB line.

[Embodiment 2]
As shown in FIGS. 7 and 9, the thin-film solid secondary battery 20 according to Embodiment 2 of the present invention includes a lower electrode 21 having either positive or negative polarity, a solid electrolyte layer 22, and an upper electrode having the other polarity. 23 are formed in this order. The lower electrode 21 includes a lower electrode active material layer 21a, a lower electrode current collector 21b, and a first terminal portion 21c. The upper electrode 23 includes an upper electrode active material layer 23a and an upper electrode current collector layer 23b. I have.
In the second embodiment, the lower electrode active material layer 21a is the “lower electrode active material” in the claims, and the lower electrode current collector 21b is the “lower electrode current collector”, the upper electrode active in the claims. The material layer 23a corresponds to “upper electrode active material” in the claims, and the upper electrode current collector layer 23b corresponds to “upper electrode current collector” in the claims.

  The lower electrode 21 is formed by sequentially laminating an insulating film 25 having an opening 25a and a notch 25b and a lower electrode active material layer 21a on a lower electrode current collector 21b made of a conductive substrate. ing. As shown in FIG. 8, the opening 25a and the notch 25b formed in the frame-like insulating film 25 are formed in a shape in which the inside of the insulating film 25 is cut out in a substantially rectangular shape.

  The lower electrode 21 is electrically connected to the first terminal portion 21c having an exposed surface extending to a position where the lower electrode active material layer 21a is not in contact with the lower electrode active material layer 21a, that is, the lower electrode current collector 21b, and the surface thereof is exposed. The first terminal portion 21c having a substantially rectangular shape is electrically connected to the conductive substrate (that is, the lower electrode current collector 21b) through the notch portion 25b. ing. In the second embodiment, the first terminal portion 21c corresponds to a “terminal portion” in the claims.

  The first terminal portion 21c is formed to be connected to various cables for external connection and the like, and a part of the insulating film 25 is cut out on the outer side in the outer peripheral direction of the lower electrode current collector 21b to form a cutout portion 25b. And the first terminal portion 21c is formed by stacking the conductive member on the notch 25b. In the second embodiment, since a part of the conductive substrate is exposed at the notch 25b formed in the insulating film 25, the notch 25b is not a configuration having a conductive member as shown in FIG. It is good also as a structure which connects various cables via this.

Furthermore, the first terminal portion 21c does not need to be partitioned by the substantially rectangular cutout portion 25b as shown in FIG. It is only necessary to have at least a configuration that maintains electrical conductivity with the lower electrode current collector 21b and a part thereof is exposed.
However, as described above, the insulating film 25, the lower electrode active material layer 21 a, the solid electrolyte layer 22, and the upper electrode are located on the outer peripheral direction outside of the lower electrode current collector 21 b and on the conductive substrate. When the notch 25b is formed on the same side as the side on which the active material layer 23a and the upper electrode current collector layer 23b are provided, various cables are connected in the same plane as the other polarity terminal, that is, the upper electrode current collector layer 23b. can do. Therefore, the thin-film solid secondary battery 20 having positive and negative terminals on the same surface can be obtained.

  Further, the opening 25 a and the notch 25 b of the insulating film 25 may be formed by being partitioned by a mask, or may be formed by etching the insulating film 25.

  The upper surface of the lower electrode active material layer 21a constituting the lower electrode 21 is formed so as to be in surface contact with the lower surface (bottom surface) of the solid electrolyte layer 22 formed on the lower electrode 21, The lower surface of the lower electrode active material layer 21 a is formed by being laminated so as to be in surface contact with the upper surface of the lower electrode current collector 21 b through the opening 25 formed in the insulating film 25.

  The lower electrode active material layer 21a, the solid electrolyte layer 22, the upper electrode active material layer 23a, and the upper electrode current collector layer 23b are laminated in substantially the same shape in plan view (substantially rectangular in the second embodiment). ing. Therefore, it is not necessary to replace the mask when forming the lower electrode active material layer 21a, the solid electrolyte layer 22, the upper electrode active material layer 23a, and the upper electrode current collector layer 23b. When the mask is exchanged, the vacuum film forming apparatus is opened to the atmosphere. However, since the same mask can be used when forming the film from the lower electrode active material layer 21a to the upper electrode current collector layer 23b, the lower electrode active material is used. The thin film solid state secondary battery 20 with good battery performance can be provided without being affected by the release of the atmosphere from the layer 21a to the upper electrode current collector layer 23b.

  The mask used when forming the film from the lower electrode active material layer 21a to the upper electrode current collector 23b may be substantially rectangular as shown in FIGS. 7 and 8, or other shapes may be used. good. Further, in the second embodiment, for connection with various cables, the first electrode layer is formed from the substantially rectangular lower electrode active material layer 21a, solid electrolyte layer 22, upper electrode active material layer 23a, and upper electrode current collector layer 23b. Two terminal portions 24 are formed to protrude in the same shape. Since various cables can be directly connected to the upper electrode current collector layer 23b by the above method, the second terminal portion 24 protrudes from the upper electrode current collector layer 23b as in the second embodiment. It does not have to be extended.

  The outer periphery of the contact surface between the lower electrode current collector 21b and the lower electrode active material layer 21a (that is, the portion defined by the opening 25a of the insulating film 25 in the lower electrode current collector 21b) is lower electrode active. It is formed inside the outer periphery of the lower surface of the material layer 21a. As shown in FIG. 9, in the thin-film solid secondary battery 20 of Embodiment 2, the lower electrode current collector 21b is in surface contact with the lower electrode active material layer 21a through the opening 25a of the insulating film 25. .

  As shown in FIG. 8, the contact surface (opening 25a) between the lower electrode current collector 21b and the lower electrode active material layer 21a includes the lower electrode active material layer 21a, the solid electrolyte layer 22, and the upper electrode active material layer. 23a and the upper electrode current collector layer 23b are formed to have a smaller area, and the upper surface of the lower electrode current collector 21b defined by the opening 25a is covered by the lower electrode active material layer 21a. Has been. That is, the entire surface of the contact surface (opening 25a) between the lower electrode current collector 21b and the lower electrode active material layer 21a is covered with the lower electrode active material layer 21a, and the outer peripheral end of the opening 25a is other. In comparison with at least the outer peripheral edge of the lower electrode active material layer 21a, the inner electrode layer (solid electrolyte layer 22, upper electrode active material layer 23a, and upper electrode current collector layer 23b) In this configuration, the outer peripheral end of the opening 25a is disposed (see FIG. 8).

  Thus, when the outer peripheral end portion of the contact surface between the lower electrode current collector 21b and the lower electrode active material layer 21a is at least inside the outer peripheral end portion of the lower electrode active material layer 21a, the lower electrode current collector is formed. The end portion of the contact surface between the electric body 21b and the lower electrode active material layer 21a is completely covered with the lower electrode active material layer 21a and the insulating film 25. Therefore, the lower electrode current collector 21b does not contact a layer formed above the solid electrolyte layer 22. As a result, a short circuit can be prevented, and the thin film solid secondary battery 20 with a high yield can be obtained.

  Regarding the material of each layer constituting the thin-film solid secondary battery 20 of the second embodiment, the description of the same materials as those of the thin-film solid secondary battery 10 of the first embodiment is omitted.

As a material of the conductive substrate having a function as the lower electrode current collector 21b, conductive glass ceramics, conductive polymer, and the like are preferably used.
In addition, as a conductive substrate, a flexible conductive substrate formed in a thin plate shape such as a film is used, and each layer is formed of a thin film of about several μm to several tens μm. A thin film solid secondary battery 20 having flexibility can be provided.

The material of the insulating film 25 formed on the conductive _substrate, evaporation method, or the like SiO 2, _Al 2 O _3, a sputtering method, a thin film was formed by a dipping method or the like, such as a polyimide film formed by a screen printing method is used It is done.

  A protective film (not shown) is provided to cover the exposed portion of the first terminal portion 21c and the portion other than the second terminal portion 24 of the thin-film solid secondary battery 20 having the above configuration. Further, as described above, the second terminal portion 24 is not specially formed, and the protective film is not provided in part on the upper electrode current collector layer 23b, and various cables are connected to the part. It is also good.

  Next, a manufacturing method for the thin-film solid secondary battery 20 according to Embodiment 2 of the present invention will be specifically described. The method for manufacturing the thin-film solid secondary battery 20 of the present invention includes a lower electrode current collector 21b, a first terminal portion 21c, a lower electrode active material layer 21a, and a solid electrode. A method of manufacturing a thin-film solid secondary battery 20 in which an electrolyte layer 22 and an upper electrode active material layer 23a and an upper electrode current collector layer 23b constituting the upper electrode 23 of the other polarity are formed in this order, An insulating film forming step for forming an insulating film 25 having an opening on the lower electrode current collector 21b made of a conductive substrate, and a frame-shaped mask for partitioning the thin film forming region are arranged on the outer periphery of the thin film forming region. Is disposed outside the outer periphery of the opening 25a of the insulating film 25 at a position where the insulating film 25 is formed on the conductive substrate, and a lower electrode is provided in the thin film formation region of the mask. Active material layer 21a and solid A solution electrolyte layer 22, and an upper electrode active material layer 23a, a film forming step of forming in this order in succession and the upper electrode collector layer 23b, in this order. Hereinafter, each step will be described in detail.

(1. Insulating film formation process)
In the method for manufacturing the thin film solid secondary battery 20 of the present invention, first, the insulating film 25 is formed on the surface of the insulating substrate constituting the lower electrode current collector 21b. At this time, the insulating film 25 is preferably formed by a sputtering method using a mask formed so that portions corresponding to the opening 25a and the notch 25b are cut off. Alternatively, the insulating film 25 may be formed on the entire surface of the conductive substrate, and the opening 25a and the notch 25b may be formed by etching. Any known method may be used for forming the insulating film 25 as long as the opening 25a and the notch 25b can be formed. At this time, instead of forming the openings 25a and notches 25b in one place on a single conductive substrate, a large number of openings 25a and notches 25b are formed. After laminating the other layers above, and dividing the entire conductive substrate, a large number of thin-film solid secondary batteries 20 can be manufactured with a small number of film formations.

(2. Mask installation process)
After the insulating film forming step is performed by the sputtering method, the inside of the vacuum film forming apparatus is opened to the atmosphere, and the mask used for forming the insulating film 25 is removed. When the opening 25a and the notch 25b are provided in the insulating film 25 by etching, a conductive substrate is set in the vacuum film forming apparatus. Note that in the case where the etching process is performed, the conductive substrate including the insulating film 25 is preferably dried and then installed in the vacuum film forming apparatus. Thereafter, a frame-like mask in which the outer peripheral end portion of the thin film forming region is disposed outside the outer peripheral end portion of the opening 25a (see FIG. 8).

(3. Film formation process)
After the mask installation step, the lower electrode active material layer 21a, the solid electrolyte layer 22, the upper electrode active material layer 23a, and the upper electrode current collector layer 23b are the same until each layer has a predetermined thickness in this order. Films are continuously formed using a mask.
In addition, after performing the said film-forming process, you may form the terminal part 21c so that it may overlap with the notch part 25b of the insulating film 25, or after performing the said insulating film film-forming process, The terminal portion 21c may be formed before forming the electrode active material layer 21a, the solid electrolyte layer 22, the upper electrode active material layer 23a, and the upper electrode current collector layer 23b.

  It is generally known that a lithium-containing oxide that is a constituent material of a lithium secondary battery is easily deteriorated by moisture and oxidation. As a countermeasure, a dry room, a glove box, etc. are required. According to the present invention, the lower electrode active material layer 11a to the upper electrode current collector layer 13b constituting the battery cell are continuously produced in a vacuum film forming apparatus. Therefore, it is suitable as a method for manufacturing a lithium secondary battery.

  Thus, by providing the opening 25a on the conductive substrate, the outer periphery of each layer above the lower electrode active material layer 21a with respect to the outer periphery of the contact surface between the lower electrode current collector 21b and the lower electrode active material layer 21a. Are formed so as to be separated from each other, and the layers after the lower electrode active material layer 21a are formed in a lump so that the outer peripheral end portions of the lower electrode current collector 21b and the upper electrode current collector layer 23b are formed. They are spaced apart. Accordingly, it is possible to prevent a short circuit due to the lower electrode current collector 21b coming into contact with the upper electrode current collector layer 23b due to “shift” of the mask or the like. Furthermore, after the lower electrode active material layer 21a is formed, it is not necessary to replace the mask before the solid electrolyte layer 22 is formed. Therefore, contamination of the lower electrode active material layer 21a can be prevented, and battery performance is improved. In addition, the manufacturing process can be simplified. Furthermore, since the conductive substrate also functions as the lower electrode current collector 21b, the thin film solid secondary battery 20 having a simple configuration can be provided.

[Embodiment 3]
As shown in FIG. 10, the thin film solid secondary battery 30 according to Embodiment 3 of the present invention includes a lower electrode 31 having either positive or negative polarity, a solid electrolyte layer 32, and an upper electrode 33 having the other polarity. They are formed in this order. The lower electrode 31 includes a lower electrode active material layer 31a, a lower electrode current collector layer 31b, and a first terminal portion 31c. The upper electrode 33 includes an upper electrode active material layer 33a and an upper electrode current collector layer 33b. It has.
In the third embodiment, the lower electrode active material layer 31a is the “lower electrode active material” in the claims, the lower electrode current collector layer 31b is the “lower electrode current collector” in the claims, the upper electrode The active material layer 33a corresponds to the “upper electrode active material” in the claims, and the upper electrode current collector layer 33b corresponds to the “upper electrode current collector” in the claims.
Since the configuration other than the first terminal portion 31c (corresponding to the “terminal portion” in the claims) is the same as the configuration of the thin-film solid secondary battery 10 of the first embodiment, description thereof is omitted. To do.

The lower electrode 31 is electrically connected to the first terminal portion 31c formed of an exposed surface extending to a position where it does not contact the lower electrode active material layer 31a, that is, the lower electrode current collector layer 31b, and its surface is exposed. The first terminal portion 31c having a substantially rectangular shape is provided, and the first terminal portion 31c is electrically connected to the lower electrode current collector layer 31b.
The first terminal portion 31c is formed so as to be connected to various cables for external connection, and is provided on the insulating substrate S on the side opposite to the side on which the lower electrode current collector layer 31b is formed. That is, the conductive member that connects the first terminal portion 31c and the lower electrode current collector layer 31b extends from the lower electrode current collector layer 31b to the back surface side through the insulating substrate S while maintaining conductivity. It is installed. Thus, even if the thin film solid secondary battery 30 of the present invention is provided with the first terminal portion 31c for connecting various cables to the side opposite to the side where each layer is provided in the insulating substrate S. good.

  As described above, when the first terminal portion 31c is formed on the back surface for each layer, a hole penetrating the insulating substrate S is provided in advance, and a conductive member is poured so as to fill the hole. The first terminal portion 31c that is conductive and exposed to the electrode current collector layer 31b can be formed.

[Embodiment 4]
As shown in FIG. 11, the thin-film solid secondary battery 40 according to Embodiment 4 of the present invention includes a lower electrode 41 having either positive or negative polarity, a solid electrolyte layer 42, and an upper electrode 43 having the other polarity. They are formed in this order. The lower electrode 41 includes a lower electrode active material layer 41a, a lower electrode current collector layer 41b, and a first terminal portion 41c. The upper electrode 43 includes an upper electrode active material layer 43a and an upper electrode current collector layer 43b. It has.
In the fourth embodiment, the lower electrode active material layer 41a is the “lower electrode active material” in the claims, the lower electrode current collector layer 41b is the “lower electrode current collector” in the claims, the upper electrode The active material layer 43a corresponds to the “upper electrode active material” in the claims, and the upper electrode current collector layer 43b corresponds to the “upper electrode current collector” in the claims.
Since the configuration other than the first terminal portion 41c (corresponding to the “terminal portion” in the claims) is the same as the configuration of the thin-film solid secondary battery 10 of Embodiment 1, the description thereof is omitted. To do.

The lower electrode 41 is electrically connected to the first terminal portion 41c formed of an exposed surface extending to a position where it does not contact the lower electrode active material layer 41a, that is, the lower electrode current collector layer 41b, and its surface is exposed. A first terminal portion 41c having a substantially rectangular shape is provided, and the first terminal portion 41c is electrically connected to the lower electrode current collector layer 41b.
The first terminal portion 41c is formed to be connected to various cables for external connection, and the conductive member passes through the side opposite to the side on which the lower electrode current collector layer 41b is formed in the insulating substrate S. And then provided on the same side as each layer. That is, the conductive member that connects the first terminal portion 41c and the lower electrode current collector layer 41b extends from the lower electrode current collector layer 41b to the back surface side through the insulating substrate S while maintaining conductivity. The first terminal portion 41c is formed on the surface side through the insulating substrate S once again. As described above, the thin-film solid secondary battery 40 of the present invention passes through the conductive member on the side opposite to the side where each layer is provided in the insulating substrate S, and then the first side on the front side of the insulating substrate S. It is good also as a structure provided with the terminal part 41c.

  Thus, when forming the 1st terminal part 41c in the back surface with respect to each layer, while providing the hole which penetrates the insulating board | substrate S beforehand and pouring a conductive member so that the hole may be filled, By forming a conductive member on the back side of the insulating substrate S so as to connect the two holes, the first terminal portion 41c that is electrically connected to the lower electrode current collector layer 41b and exposed. Can be formed.

[Embodiment 5]
As shown in FIG. 12, the thin film solid secondary battery 50 according to the fifth embodiment of the present invention includes a lower electrode 51 having one of positive and negative polarities, a solid electrolyte layer 52, and an upper electrode 53 having the other polarity. They are formed in this order. The lower electrode 51 includes a lower electrode active material layer 51a, a lower electrode current collector 51b, and a first terminal portion 51c. The upper electrode 53 includes an upper electrode active material layer 53a and an upper electrode current collector layer 53b. I have.
In the fifth embodiment, the lower electrode active material layer 51a is the “lower electrode active material” in the claims, and the lower electrode current collector 51b is the “lower electrode current collector” in the claims. The material layer 53a corresponds to “upper electrode active material” in the claims, and the upper electrode current collector layer 53b corresponds to “upper electrode current collector” in the claims.

  The lower electrode 51 is formed by sequentially laminating an insulating film 55 having an opening 55a and a lower electrode active material layer 51a on a lower electrode current collector 51b made of a conductive substrate. The opening 55a formed in the frame-like insulating film 55 is formed in a shape in which the inner side of the insulating film 55 is cut into a substantially rectangular shape, as in the second embodiment.

The lower electrode 51 is provided with a substantially rectangular first terminal portion 51c which is electrically connected to the lower electrode current collector 51b and whose surface is exposed on the back side (side where each layer is not formed) of the conductive substrate. The first terminal portion 51c is provided on the back surface of the conductive substrate (that is, the lower electrode current collector 51b). In the fifth embodiment, the first terminal portion 51c corresponds to a “terminal portion” in the claims.
The first terminal portion 51c is configured by an exposed surface from which at least a part of the lower electrode current collector 51b is exposed. If various cables can be connected to the back surface of the conductive substrate constituting the lower electrode current collector 51b, the first terminal portion 51c is at least electrically conductive with the lower electrode current collector 51b. Any part of the structure may be exposed. Accordingly, the position of the first terminal portion 51c is not limited as long as it is on the back surface of the conductive substrate constituting the lower electrode current collector 51b. For example, the first terminal portion 51c may be formed by covering the back side of the conductive substrate with a protective film and cutting away a part of the protective film.

  As described above, in the thin-film solid secondary battery 50 of Embodiment 5, the lower electrode current collector 51b is configured by the conductive substrate, and the lower electrode current collector 51b is further formed by the insulating film 55 provided on the conductive substrate. Since the contact surface between the lower electrode active material layer 51a and the lower electrode active material layer 51a is adjusted, the lower electrode current collector 51b and the upper electrode current collector layer 53b do not contact each other. Furthermore, according to the configuration of the fifth embodiment, the thin-film solid secondary battery 50 can be connected with a high degree of freedom with respect to the connection position of various cables as long as it is on the back side of the conductive substrate. A thin film solid secondary battery 50 that is simple and extremely efficient in production can be provided.

[Embodiment 6]
In the first to fifth embodiments, the case where the cell is a single-layer single cell has been described as an example. However, the thin-film solid secondary batteries 10, 20, 30, 40, and 50 are arranged in series, in parallel. A connected configuration may be used.
A thin film solid secondary battery 60 according to Embodiment 6 of the present invention is an example in which two thin film solid secondary batteries are stacked as shown in FIG. The thin film solid secondary battery 60 includes a lower electrode 61 having one of positive and negative polarities, a solid electrolyte layer 62, and an upper electrode 63 having the other polarity, which are formed in this order. An active material layer 61a ′, a solid electrolyte layer 62 ′, and an upper electrode 63 ′ are provided. The lower electrode 61 formed on the substrate S side includes a lower electrode active material layer 61a, a lower electrode current collector layer 61b, and a first terminal portion 61c. The upper electrode 63 includes an upper electrode active material layer. 63a, and an upper electrode current collector layer 63b. Further, the upper electrode 63 ′ stacked above includes an upper electrode active material layer 63a ′ and an upper electrode current collector layer 63b ′.
In the sixth embodiment, the lower electrode active material layers 61a and 61a ′ are “lower electrode active material” in the claims, and the lower electrode current collector 61b is “lower electrode current collector” in the claims, The upper electrode active material layers 63a and 63a ′ correspond to “upper electrode active material” in the claims, and the upper electrode current collector layers 63b and 63a ′ correspond to “upper electrode current collectors” in the claims.

  And as shown in FIG. 13, the edge part of the lower electrode collector layer 61a is covered with lower electrode active material layer 61a 'arrange | positioned upwards (that is, lower electrode collector layer 61a and lower electrode active material layer). The outer periphery of the contact surface with the material layer 61a ′ is formed inside the outer periphery of the lower surface of the lower electrode active material layer 61a ′), so that the lower electrode current collector layer 61a and the upper electrode current collector layer are formed. 63b 'do not contact each other. Therefore, the thin film solid secondary battery 60 of the present invention is configured to prevent conduction between the lower electrode current collector layer 61a and the upper electrode current collector layer 63b ′, and a plurality of thin film solid secondary batteries are stacked in multiple stages. Can also be applied.

  The manufacturing method of the thin film solid secondary battery 60 of the sixth embodiment is the same as that of the manufacturing method of the first embodiment (FIG. 3), with the mask having a slightly larger opening at the end of film formation of the upper electrode current collector layer 13b. It further has a process of exchanging. After the mask replacement, the second (upper) lower electrode active material layer 61a ′, solid electrolyte layer 62 ′, upper electrode active material layer 63a ′, and upper electrode current collector layer 63b ′ are stacked in this order. To do. When the second lower electrode active material layer 61a ′ is a positive electrode and the upper electrode 63 ′ (upper electrode active material layer 63a ′, upper electrode current collector layer 63b ′) is a negative electrode, the thin film solid secondary layer is obtained. The battery is connected in series. Therefore, the uppermost layer constituting the thin film solid-state secondary battery provided in the uppermost stage (second stage in the present embodiment), that is, the upper electrode current collector layer 63b ′ constitutes the second terminal portion (not shown). It only has to be.

[Embodiment 7]
Moreover, the shape and arrangement position of the first terminal portions 11c, 21c, 31c, 41c, 51c, 61c and the second terminal portions 14, 24 are not limited to the above embodiment, and are electrically connected to each current collector. It may be formed in any shape and position as long as it is exposed so that various cables can be connected.

  Therefore, as shown in FIG. 14, the thin film solid secondary battery 70 according to Embodiment 7 of the present invention includes a lower electrode current collector layer 71b, a lower electrode active material layer 71a, a solid electrolyte layer 72, and an upper electrode active material layer. 73a and an upper electrode current collector layer 73b are stacked in a substantially rectangular shape in plan view, and the first terminal portion 71c exposed at one apex portion and the second terminal portion 74 at the other apex portion are formed. It is good also as a structure which provided. The first terminal portion 71c is exposed to the atmosphere by having a shape in which the apex portions of the lower electrode active material layer 71a, the solid electrolyte layer 72, the upper electrode active material layer 73a, and the upper electrode current collector layer 73b are missing. It becomes composition. Further, the second terminal portion 74 has a shape in which the apex portion of the lower electrode current collector layer 71b is missing, and is disposed so as to extend outside the lower electrode current collector layer 71b. And it forms into the film so that the outer peripheral edge part of the lower electrode collector layer 71b may become inside the outer peripheral edge part of the lower electrode active material layer 71a. Note that the stacking order of the layers is the same as that of the thin film solid secondary battery 10.

In addition, although Embodiment 6 was mentioned as an example regarding the structure which connects the thin film solid secondary battery laminated | stacked in multiple steps, the connection form is not limited to this, Various other forms can be taken. For example, each thin film solid state secondary battery is configured in such a manner that the first stage thin film solid state secondary battery is laminated from the positive electrode, the polarity is alternately changed so that the second stage is from the negative electrode, and the third stage is from the positive electrode. Secondary batteries may be stacked so that they are connected in parallel. At this time, the positive electrode terminal portion and the negative electrode terminal portion of the thin-film solid secondary battery at each stage are arranged for each stacked stage, and have the same polarity as the thin-film solid secondary battery stacked immediately below (or directly above). Each of the terminals is formed to be conductive.
Further, each layer constituting the battery does not necessarily have to be rectangular as in the first to seventh embodiments, and may be formed of a thin film having a certain area.

  The thin-film solid-state secondary battery manufactured according to the present invention can be used as a power source for a composite apparatus equipped with a device, thereby driving the device stably for a long time. Examples of such devices include mobile devices such as mobile phones, notebook computers, digital cameras, and portable games.

S Insulating substrate 10, 20, 30, 40, 50, 60, 70 Thin film solid secondary battery 11, 21, 31, 41, 51, 61 Lower electrode 11a, 21a, 31a, 41a, 51a, 61a, 61a ', 71a Lower electrode active material layer (lower electrode active material)
11b, 31b, 41b, 61b, 71b Lower electrode current collector layer (lower electrode current collector)
21b, 51b Lower electrode current collector (conductive substrate)
11c, 21c, 31c, 41c, 51c, 61c, 71c First terminal portion (terminal portion)
12, 22, 32, 42, 52, 62, 62 ', 72 Solid electrolyte layer (solid electrolyte)
13, 23, 33, 43, 53, 63, 63 'Upper electrode 13a, 23a, 33a, 43a, 53a, 63a, 63a', 73a Upper electrode active material layer (upper electrode active material)
13b, 23b, 33b, 43b, 53b, 63b, 63b ′, 73b Upper electrode current collector layer (upper electrode active material)
14, 24, 74 Second terminal portion 25, 55 Insulating film 25a, 55a Opening portion 25b Notch portion 100 Thin-film solid secondary battery (comparative example)
110 Lower electrode 110a Lower electrode active material layer 110b Lower electrode current collector layer 110c First terminal portion 120 Solid electrolyte layer 130 Upper electrode 130a Upper electrode active material layer 130b Upper electrode current collector layer

Claims (8)

A thin-film solid secondary battery in which a lower electrode of either positive or negative polarity, a solid electrolyte, and an upper electrode of the other polarity are formed in this order,
The lower electrode includes a lower electrode active material in surface contact with the lower surface of the solid electrolyte, a lower electrode current collector in surface contact with the lower surface of the lower electrode active material, and the lower electrode current collector and the lower electrode current collector. An exposed surface that is extended and exposed to a position not in surface contact with the electrode active material, or a terminal portion that is an exposed surface where at least a part of the lower electrode current collector is exposed, and
The upper electrode comprises an upper electrode active material in surface contact with the upper surface of the solid electrolyte, and an upper electrode current collector in surface contact with the upper surface of the upper electrode active material,
The lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector are laminated in substantially the same shape in plan view,
A thin-film solid secondary battery, wherein an outer periphery of a contact surface between the lower electrode current collector and the lower electrode active material is formed inside an outer periphery of a lower surface of the lower electrode active material.   2. The thin film solid state secondary battery according to claim 1, wherein the lower electrode current collector and the terminal portion are conductor film patterns formed on a thin plate-like insulating substrate having flexibility. .   3. The thin film solid state secondary battery according to claim 1, wherein the terminal portion extends outward in the outer circumferential direction of the lower electrode current collector. The lower electrode current collector is made of a conductive substrate,
An insulating film having an opening is formed on the conductive substrate,
The thin film solid secondary battery according to claim 1, wherein an outer periphery of the opening of the insulating film is formed inside an outer periphery of the lower electrode active material. The lower electrode active material is made of a material containing lithium,
The solid electrolyte is composed of lithium phosphate (Li ₃ PO ₄ ), lithium phosphate oxynitride (LiPON) obtained by partially replacing oxygen of lithium phosphate with nitrogen, or a composite oxide containing a transition metal and Li and N 5. The thin film solid secondary battery according to claim 1, wherein the thin film solid secondary battery is any one selected. Lower electrode current collector, terminal portion and lower electrode active material constituting the lower electrode of either positive or negative polarity, solid electrolyte, upper electrode active material and upper electrode current collector constituting the other polarity upper electrode Is a method of manufacturing a thin film solid secondary battery formed in this order,
On the insulating substrate, forming a conductive film pattern that constitutes the lower electrode current collector and the terminal portion that is electrically connected to the lower electrode current collector and at least partially exposed;
A frame-shaped mask that partitions the thin film formation region, wherein the outer periphery of the thin film formation region is outside the outer periphery of the lower electrode current collector and a part of the terminal portion is not included in the thin film formation region A step of disposing the conductive film pattern on the insulating substrate on the side where the conductive film pattern is formed;
Depositing the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector in this order in the thin film formation region of the mask;
A method for producing a thin-film solid secondary battery, comprising: Lower electrode current collector, terminal portion and lower electrode active material constituting the lower electrode of either positive or negative polarity, solid electrolyte, upper electrode active material and upper electrode current collector constituting the other polarity upper electrode Is a method of manufacturing a thin film solid secondary battery formed in this order,
Forming an insulating film having an opening on the surface of the conductive substrate constituting the lower electrode current collector; and
A frame-shaped mask that partitions the thin film formation region is disposed on the side of the conductive substrate on which the insulating film is formed at a position where the outer periphery of the thin film formation region is outside the outer periphery of the opening. Process,
Depositing the lower electrode active material, the solid electrolyte, the upper electrode active material, and the upper electrode current collector in this order in the thin film formation region of the mask;
A method for producing a thin-film solid secondary battery, comprising: The lower electrode active material is made of a material containing lithium,
The solid electrolyte is composed of lithium phosphate (Li ₃ PO ₄ ), lithium phosphate oxynitride (LiPON) obtained by partially replacing oxygen of lithium phosphate with nitrogen, or a composite oxide containing a transition metal and Li and N. The method for producing a thin-film solid secondary battery according to claim 6, wherein the method is any one selected.

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