JP2014229502A - Manufacturing method of all-solid state lamination battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an all-solid state lamination battery free from limitations of the type of solid electrolyte and capable of reducing manufacturing loss.SOLUTION: A first unit 10 and a second unit 10 each having a structure, in which a solid electrolyte layer 13 and an active material layer 14 are disposed between a pair of metal layers 11 and 15, are prepared. The second unit 10 is laminated on the first unit 10 to form an electrical connection in series between the first unit 10 and the second unit 10. With this, an all-solid state lamination battery 30 is obtained.

Description

  The present invention relates to a method for manufacturing a laminated all solid state battery.

  Lithium ion secondary batteries have features such as high energy density and high voltage operation. Therefore, lithium ion secondary batteries are used in information devices such as mobile phones as small and light secondary batteries. In recent years, the demand for lithium ion secondary batteries is increasing as a large power source such as a power source of a hybrid vehicle.

  A lithium ion secondary battery is composed of a positive electrode, a negative electrode, and an electrolyte disposed therebetween. The electrolyte is a non-aqueous electrolyte solution or a solid electrolyte. Since widely used electrolytes are flammable, a system to ensure safety is essential. On the other hand, since the solid electrolyte is nonflammable, the above system can be simplified. Hereinafter, a lithium ion secondary battery using a solid electrolyte is referred to as an “all-solid battery”.

  When a high voltage is required as in a hybrid vehicle, a lithium ion secondary battery using an electrolytic solution requires a partition wall disposed between the cells like a lead storage battery, for example. Alternatively, a battery case is required for each cell. When a plurality of cells are simply connected in series, the electrolyte is shared between the cells, and a high voltage cannot be obtained. On the other hand, the electrolyte of an all-solid battery does not have fluidity, and the electrolyte is not shared between cells. Therefore, according to the all solid state battery, a high voltage can be obtained by simply connecting a plurality of cells in series. Hereinafter, such a secondary battery is referred to as a “stacked all-solid battery”.

  As shown in FIG. 5, the all-solid-state battery described in Patent Document 1 includes a current collector 302, a positive electrode active material layer 303, a solid electrolyte layer 304, and a negative electrode active material layer 305 in this order on a substrate 301. It is obtained by forming.

  As shown in FIG. 6, the stacked all solid state battery described in Patent Document 2 is obtained by integrating the unit 421, the unit 422, and the unit 423 so that the solid electrolyte layer 403 is in contact with each other. The unit 421 includes a current collector 401, a negative electrode 402, and a solid electrolyte layer 403. The unit 422 includes a solid electrolyte layer 403, a positive electrode 404, a current collector 401, a negative electrode 402, and a solid electrolyte layer 403. The unit 423 includes a current collector 401, a positive electrode 404, and a solid electrolyte layer 403.

JP 2008-159399 A JP 2008-13285 A

  According to the structure shown in FIG. 5, when a layer is peeled off and a defect such as a pinhole occurs when the layers are sequentially formed on the substrate, the whole including the layer in which the defect has occurred becomes a defective product. . Therefore, manufacturing loss tends to be large. According to the structure shown in FIG. 6, it is necessary to join the solid electrolyte layer and the solid electrolyte layer. In order to achieve good bonding, the type of solid electrolyte is limited.

  An object of the present disclosure is to provide a technique that is not easily limited by the type of solid electrolyte and that can reduce manufacturing loss.

That is, this disclosure
Producing a first unit and a second unit each having a structure in which a solid electrolyte layer and an active material layer are disposed between a pair of metal layers;
Laminating the second unit on the first unit such that the first unit and the second unit form an electrical series connection;
A method for producing a laminated all solid state battery is provided.

  The above manufacturing method is not easily limited by the type of solid electrolyte, and can reduce manufacturing loss.

Schematic cross-sectional view of the laminated all solid state battery of the first embodiment Schematic sectional view of the laminated all solid state battery of Modification 1 Schematic cross-sectional view of the laminated all solid state battery of the second embodiment Schematic sectional view of the laminated all solid state battery of Modification 2 Schematic cross-sectional view of a conventional all-solid battery Schematic sectional view of another conventional all-solid battery

  The reason why the method described in Patent Document 2 (see FIG. 6) is easily restricted by the type of solid electrolyte is as follows. In the case where the solid electrolyte layer is made of a flexible sulfide-based solid electrolyte, a good interfacial junction can be formed between the solid electrolyte layer and the solid electrolyte layer. However, when the solid electrolyte layer is made of a hard oxide solid electrolyte, it is difficult to form an interface junction, resulting in a large grain boundary resistance. Therefore, in order to join the solid electrolyte layer and the solid electrolyte layer, a sintering process at an extremely high temperature is indispensable. When sintering is performed at a high temperature, interdiffusion of elements occurs at the interface between the positive electrode and the solid electrolyte layer or the interface between the negative electrode and the solid electrolyte layer, and a layer having a large resistance may be newly generated.

The first aspect of the present disclosure is:
Producing a first unit and a second unit each having a structure in which a solid electrolyte layer and an active material layer are disposed between a pair of metal layers;
Laminating the second unit on the first unit such that the first unit and the second unit form an electrical series connection;
A method for producing a laminated all solid state battery is provided.

  According to the first aspect, when the first unit and the second unit are produced, the quality of each unit can be determined. That is, since defective units can be eliminated before the stacking process, production loss is suppressed as much as possible. Further, the second unit is stacked on the first unit so as to form an electrical series connection. At this time, the metal layer of the second unit is in contact with the metal layer of the first unit. Therefore, the method of the first aspect is not easily limited by the type of solid electrolyte. As a result, it is possible to efficiently manufacture a stacked all-solid battery having a high energy density.

  According to a second aspect of the present disclosure, in addition to the first aspect, the pair of metal layers includes a first metal layer and a second metal layer formed by different methods, and the first unit of the first unit includes Provided is a method for manufacturing a stacked all solid state battery, wherein the stacking step is performed so that the second metal layer of the second unit is in contact with the metal layer. Even if the first metal layer and the second metal layer are formed by different methods, a plurality of units can be easily stacked by bringing the metal layers into contact with each other.

  According to a third aspect of the present disclosure, in addition to the first or second aspect, the pair of metal layers includes a first metal layer and a second metal layer formed by different methods, and the first unit and In the step of producing the second unit, there is provided a method for producing a stacked all solid state battery, wherein a metal foil or a metal thin plate is used as the first metal layer, and the second metal layer is formed by a film forming method. When the first metal layer is self-supporting like a foil or a thin plate, the first metal layer can be used as a substrate. According to the third aspect, the second metal layer can be easily formed on the solid electrolyte layer or the active material layer.

  According to a fourth aspect of the present disclosure, in addition to the second or third aspect, there is provided a method for manufacturing a stacked all solid state battery, wherein the thickness of the second metal layer is smaller than the thickness of the first metal layer. By making the second metal layer sufficiently thin, the energy density of the stacked all-solid battery can be increased.

  According to a fifth aspect of the present disclosure, in addition to any one of the first to fourth aspects, the pair of metal layers includes a first metal layer and a second metal layer formed by different methods, In the step of manufacturing the first unit and the second unit, the first metal layer is brought into contact with one main surface of the solid electrolyte layer, and the active material layer is brought into contact with the other main surface of the solid electrolyte layer A method for manufacturing a laminated all solid state battery is provided. According to such a structure, it is possible to increase the energy density of the laminated all solid state battery.

  In a sixth aspect of the present disclosure, in addition to any one of the first to fifth aspects, the pair of metal layers includes a first metal layer and a second metal layer formed by different methods, In the step of manufacturing the first unit and the second unit, a method of forming the solid electrolyte layer, a method of forming the active material layer, and a method of forming the second metal layer are respectively a sputtering method and a vapor deposition method. A method for producing a laminated all-solid-state battery, which is a thermal spray method, a cold spray method, or an aerosol deposition method. These film forming methods can also be suitably employed when forming a solid electrolyte layer using an oxide-based solid electrolyte. Moreover, according to these film-forming methods, the adhesiveness between a solid electrolyte layer and an active material layer can fully be improved.

  According to a seventh aspect of the present disclosure, in addition to the sixth aspect, the method of forming the solid electrolyte layer and the method of forming the active material layer are a thermal spray method, a cold spray method, or an aerosol deposition method. A method for manufacturing an all-solid battery is provided. According to these film forming methods, the solid electrolyte layer and the active material layer can be formed under relatively low temperature conditions.

  In an eighth aspect of the present disclosure, in addition to any one of the first to seventh aspects, when the active material layer is defined as a first active material layer, the first unit and the second unit are produced. A second active material having an operating potential different from that of the first active material layer and a polarity opposite to that of the first active material layer, and separated from the first active material layer via the solid electrolyte layer Provided is a method for manufacturing a laminated all-solid battery, in which a layer is further formed. According to such a configuration, an element (for example, lithium or sodium) moves between the first active material layer and the second active material layer. Therefore, the fluctuation | variation of the volume of the 1st unit and 2nd unit accompanying charging / discharging can be suppressed.

The ninth aspect of the present disclosure is:
A first unit having a structure in which a solid electrolyte layer and an active material layer are disposed between the first metal layer and the second metal layer;
A second unit that has a structure in which the solid electrolyte layer and the active material layer are disposed between the first metal layer and the second metal layer, and is stacked on the first unit;
With
The thickness of the second metal layer is smaller than the thickness of the first metal layer,
Provided is a stacked all solid state battery in which the first unit is stacked on the second unit so that the first unit and the second unit form an electrical series connection.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, this invention is not limited by the following embodiment.

(First embodiment)
As shown in FIG. 1, the stacked all-solid battery 30 (hereinafter referred to as “battery 30”) of the present embodiment is formed by stacking a plurality (two in FIG. 1) of units 10. The unit 10 includes a first metal layer 11, a solid electrolyte layer 13, an active material layer 14 (positive electrode active material layer), and a second metal layer 15, and is formed by laminating these layers in this order. . That is, the unit 10 has a structure in which the solid electrolyte layer 13 and the active material layer 14 are disposed between the pair of metal layers 11 and 15. In the unit 10, the solid electrolyte layer 13 is in contact with the first metal layer 11, and the active material layer 14 is in contact with the second metal layer 15. The solid electrolyte layer 13 plays a role of a separator, and electrically separates the first metal layer 11 and the active material layer 14.

  At the time of charging, lithium or sodium is detached from the active material layer 14. Lithium or sodium is conducted through the solid electrolyte layer 13 and deposited on the first metal layer 11. Specifically, lithium or sodium is deposited between the first metal layer 11 and the solid electrolyte layer 13. At the time of discharging, lithium or sodium conducts through the solid electrolyte layer 13 and is inserted (occluded) into the active material layer 14.

  Next, a method for manufacturing the battery 30 will be described.

  First, a plurality of units 10 are produced. Specifically, the solid electrolyte layer 13, the active material layer 14, and the second metal layer 15 are formed in this order on the first metal layer 11 by an arbitrary film forming method. Thereby, the unit 10 is obtained.

  As a metal material for forming the first metal layer 11, a metal material that is difficult to be alloyed with an alkali metal such as lithium or sodium can be used. Examples of such a metal material include nickel, iron, copper, platinum, an alloy containing one selected from these as a main constituent element, and stainless steel. The first metal layer 11 is preferably a foil made of the above metal material or a thin plate made of the above metal material. In the case where the first metal layer 11 is self-supporting like a foil or a thin plate, the first metal layer 11 can be used as a substrate in a film forming step described later. In addition, the use of metal foil or metal thin plate is excellent in terms of cost and productivity. In the present specification, the “main constituent element” means an element contained in the largest amount by mass ratio. There is no significant difference between the metal foil and the metal thin plate. For example, a thickness of less than 100 μm can be defined as a foil, and a thickness of 100 μm or more as a thin plate. Moreover, what is bent by its own weight can be defined as foil, and what is not bent is defined as thin plate. From the viewpoint of volume energy density, it is advantageous to use a metal foil.

As the solid electrolyte for forming the solid electrolyte layer 13, lithium ion or sodium ion conductive solid electrolyte can be used. Examples of the lithium ion conductive solid electrolyte include Li ₃ Zr ₂ Si ₂ PO ₁₂ , Li ₇ La ₃ Zr ₂ O ₁₂ , Li ₅ La ₃ Ta ₂ O ₁₂ , Li _{1 + x} Al _x Ti _{2 -x} (PO ₄ ). ₃ , Li _1.5 Ti _1.7 Al _0.8 P _2.8 Si _0.2 O ₁₂ , La _{2 / 3-x} Li _3x TiO ₃ , Li ₂ S—SiS ₂ glass, Li ₂ S—P ₂ S ₅ glass, Li ₂ S— Examples thereof include P ₂ S ₅ glass ceramics, Li ₂ S—B ₂ S ₃ glass, Li _3.25 Ge _0.25 P _0.75 S ₄ , and Li ₁₀ GeP ₂ S ₁₂ . Examples of the sodium ion conductive solid electrolyte include β-Al ₂ O ₃ , Na _1.3 Zr ₂ Si _0.3 P _2.7 O ₁₂ , Na ₃ Zr ₂ Si ₂ PO ₁₂ , and Na ₃ PS ₃ .

  The solid electrolyte layer 13 can be formed by a film forming method (specifically, a film forming method in a gas phase) such as a sputtering method, a vapor deposition method, a thermal spray method, a cold spray method, or an aerosol deposition method. These film forming methods can also be suitably employed when the solid electrolyte layer 13 is formed using an oxide-based solid electrolyte. These film forming methods are also effective in reducing the grain boundary resistance. In order to obtain a molded body using an oxide-based solid electrolyte, a sintering process at a high temperature is generally required. However, according to the film forming method described above, such a sintering step can be omitted.

  Since a high film forming temperature is not required, a thermal spray method, a cold spray method or an aerosol deposition method is desirable as a method for forming the solid electrolyte layer 13. By forming the solid electrolyte layer 13 under a low temperature condition, it is possible to prevent changes such as a change in crystal phase, amorphization, and crystallization of the amorphous phase from occurring in the solid electrolyte. In other words, the solid electrolyte can be prevented from deteriorating in the film forming process. As a result, the original characteristics of the solid electrolyte are reliably exhibited even after film formation. Furthermore, the thermal spray method, the cold spray method, and the aerosol deposition method can achieve a high film formation rate, and are suitable for manufacturing a large-capacity unit 10.

The active material for forming the active material layer 14 includes an alkali metal such as a transition metal oxide containing lithium, a transition metal sulfide containing lithium, a transition metal oxide containing sodium, or a transition metal sulfide containing sodium. Transition metal compounds can be used. Examples of the transition metal oxide containing lithium include LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiNi _1-x Mn _x O ₂ (0 <x ≦ 1), LiNi _1-xy Mn _x Co _y O ₂ (0 < x ≦ 1, 0 <y ≦ 1, 0 <x + y ≦ 1), LiNi _1-xy Co _x Al _y O ₂ (0 <x ≦ 1, 0 <y ≦ 1, 0 <x + y ≦ 1) and the like. . Examples of the transition metal sulfide containing lithium include LiTiS ₂ and LiMoS ₂ . Examples of transition metal oxides containing sodium include NaCoO ₂ , NaFeO ₂ , NaFe _0.4 Mn _0.3 Ni _0.3 O ₂ , NaCrO ₂ , Na _2/3 Fe _0.5 Mn _0.5 O ₂ , Na ₂ FePO ₄ F, Na ₃ V ₂ ( PO ₄ ) ₂ F ₃ , NaVPO ₄ F, Na ₄ Mn ₃ (PO ₄ ) ₂ (P ₂ O ₇ ), NaFeF _{3 and the} like. Examples of the transition metal sulfide containing sodium include NaTiS ₂ and NaMoS ₂ .

  The active material layer 14 can be formed by a film forming method (specifically, a film forming method in a gas phase) such as a sputtering method, a vapor deposition method, a thermal spray method, a cold spray method, or an aerosol deposition method. According to these methods, the adhesion between the solid electrolyte layer 13 and the active material layer 14 can be sufficiently enhanced.

  Since a high film forming temperature is not required, a thermal spray method, a cold spray method, or an aerosol deposition method is desirable as a method for forming the active material layer 14. By forming the active material layer 14 under a low temperature condition, it is possible to prevent changes such as a change in crystal phase, amorphization, and crystallization of the amorphous phase from occurring in the active material. In other words, it is possible to prevent the active material from being deteriorated in the film forming process. As a result, the original characteristics of the active material are reliably exhibited even after film formation.

  As a metal material for forming the second metal layer 15, a metal material that is difficult to be alloyed with an alkali metal such as lithium or sodium can be used. Examples of such a metal material include nickel, iron, copper, platinum, an alloy containing one selected from these as a main constituent element, and stainless steel.

  Similar to the solid electrolyte layer 13 and the active material layer 14, the second metal layer 15 is formed by a film forming method such as a sputtering method, a vapor deposition method, a thermal spray method, a cold spray method, an aerosol deposition method (specifically, a gas phase In a film forming method). According to these film forming methods, the second metal layer 15 can be easily formed on the active material layer 14. In addition, even if a high temperature is applied to the metal material, the characteristics of the metal material are often not greatly affected. Therefore, the temperature condition when forming the second metal layer 15 is relatively gentle. However, in order to avoid adverse effects on the solid electrolyte layer 13 and the active material layer 14, the second metal layer 15 is also preferably formed by a thermal spray method, a cold spray method, or an aerosol deposition method. The second metal layer 15 can also be formed by a wet film forming method. For example, the second metal layer 15 can be formed by applying a conductive paste on the active material layer 14. Furthermore, the second metal layer 15 can be formed by bonding a metal foil on the active material layer 14.

  The main metal element contained in the second metal layer 15 may be the same as the main metal element contained in the first metal layer 11. The composition of the second metal layer 15 may be the same as the composition of the first metal layer 11. In the present embodiment, the difference between the first metal layer 11 and the second metal layer 15 is that these metal layers 11 and 15 are formed by different methods. The metal foil or metal thin plate as the first metal layer 11 is obtained by rolling. The second metal layer 15 can be formed by a film forming method in a gas phase. Therefore, the thickness of the second metal layer 15 is smaller than the thickness of the first metal layer 11. The ratio (t2 / t1) of the thickness t2 of the second metal layer 15 to the thickness t1 of the first metal layer 11 satisfies the relationship of 1/1000 ≦ (t2 / t1) <1, for example. By making the second metal layer 15 sufficiently thin, the energy density of the battery 30 can be increased. Of course, the thickness of the second metal layer 15 may be equal to the thickness of the first metal layer 11. The “major metal element” means a metal element contained in the largest amount by mass ratio.

  The solid electrolyte layer 13, the active material layer 14, and the second metal layer 15 may all be formed by the same film formation method (for example, aerosol deposition method), or may be formed by different film formation methods.

  The unit 10 is obtained through the above film forming process. A plurality of units 10 are manufactured, and the plurality of units 10 are stacked so that the plurality of units 10 form an electrical series connection. As shown in FIG. 1, when the solid electrolyte layer 13 and the active material layer 14 are disposed between the first metal layer 11 and the second metal layer 15, the first metal of a unit 10 (first unit). The laminating process can be performed such that the second metal layer 15 of another unit 10 (second unit) is in contact with the layer 11. Thereby, the battery 30 is obtained. Even if the first metal layer 11 and the second metal layer 15 are formed by different methods, the plurality of units 10 can be easily stacked by bringing the metal layers into contact with each other. By increasing the number of units 10, the voltage of the battery 30 can be increased.

  Electrical connection between adjacent units 10 is achieved simply by bringing the metal layers into contact with each other. However, the plurality of units 10 may be joined or connected via a conductive layer having adhesiveness. In this way, it is possible to prevent the unit 10 from being displaced. The conductive layer can typically be formed by a conductive double-sided tape or a conductive paste.

  In the present embodiment, in the step of manufacturing the unit 10, the first metal layer 11 is brought into contact with one main surface (for example, the lower surface) of the solid electrolyte layer 13, and the other main surface (for example, the upper surface) of the solid electrolyte layer 13. ) Is brought into contact with the active material layer 14. According to such a structure, the energy density of the battery 30 can be increased.

  According to the method of the present embodiment, not only can the characteristic variation be managed for each unit 10, but also an inspection for finding a defective product can be easily performed for each unit 10. That is, it is possible to find a defective product when the unit 10 is manufactured. This contributes to a reduction in manufacturing loss. Further, the area of the unit 10 can be increased without depending on the type of the solid electrolyte. As a result, the battery 30 having a high energy density can be provided.

  Hereinafter, Modification Example 1, Second Embodiment, and Modification Example 2 will be described. Elements common to the battery 30 shown in FIG. 1 and the following modification or embodiment are denoted by the same reference numerals, and description thereof is omitted.

(Modification 1)
As shown in FIG. 2, the stacked all-solid battery 30a is formed by alternately stacking units 10 and units 10a. In the unit 10a, the first metal layer 11, the active material layer 14, the solid electrolyte layer 13, and the second metal layer 15 are laminated in this order. That is, the arrangement of the solid electrolyte layer 13 and the active material layer 14 between the first metal layer 11 and the second metal layer 15 is not limited. In the unit 10 a, the active material layer 14 is in contact with the first metal layer 11, and the solid electrolyte layer 13 is in contact with the second metal layer 15. This arrangement is opposite to the arrangement of the solid electrolyte layer 13 and the active material layer 14 in the unit 10.

  In the battery 30a, the first metal layers 11 are in contact with each other directly or through a conductive layer, and the second metal layers 15 are in contact with each other directly or through a conductive layer. Furthermore, it is also possible to obtain a stacked all solid state battery using only the plurality of units 10a.

(Second Embodiment)
As shown in FIG. 3, the battery 40 of the present embodiment is formed by stacking a plurality of (two in FIG. 3) units 20. The unit 20 includes a first metal layer 11, a second active material layer 12 (negative electrode active material layer), a solid electrolyte layer 13, a first active material layer 14 (positive electrode active material layer), and a second metal layer 15. These layers are formed by laminating in this order. In the unit 20, the second active material layer 12 is in contact with the first metal layer 11, and the first active material layer 14 is in contact with the second metal layer 15.

  That is, the unit 20 is obtained by adding the second active material layer 12 to the unit 10 described with reference to FIG. The second active material layer 12 has an operating potential different from that of the first active material layer 14 and a polarity opposite to that of the first active material layer 14. In the present embodiment, the first active material layer 14 is a positive electrode active material layer, and the second active material layer 12 is a negative electrode active material layer. The second active material layer 12 is electrically separated from the first active material layer 14 by the solid electrolyte layer 13. According to such a configuration, lithium or sodium moves between the first active material layer 14 and the second active material layer 12. Therefore, the fluctuation | variation of the volume of the unit 20 accompanying charging / discharging can be suppressed. The “operation potential” means a reduction potential of the first active material layer 14 or the second active material layer 12 with respect to a reference potential (for example, a reduction potential of lithium).

As a material (second active material) for forming the second active material layer 12, an alkali metal such as metal lithium or metal sodium can be used. Furthermore, compounds capable of inserting and extracting lithium ions or sodium ions can also be used. For example, graphite, hard carbon, silicon, silicon oxide, metal silicide, tin, tin oxide, tin alloy, indium, indium alloy, germanium, germanium alloy, aluminum, aluminum alloy, Li [Li _1/3 Ti _5/3 ] O ₄ , titanium disulfide, molybdenum disulfide, and the like can be used.

The second active material layer 12 can also be formed by a film forming method (film forming method in a gas phase) such as a sputtering method, a vapor deposition method, a thermal spray method, a cold spray method, or an aerosol deposition method. Since a high film forming temperature is not required, a thermal spray method, a cold spray method, or an aerosol deposition method is desirable as a method for forming the second active material layer 12. By forming the second active material layer 12 under a low temperature condition, it is possible to prevent changes such as a change in crystal phase, amorphization, and crystallization of the amorphous phase from occurring in the active material. In other words, it is possible to prevent the active material from being deteriorated in the film forming process. As a result, the original characteristics of the active material are reliably exhibited even after film formation. In particular, when a material that is easily affected by heat, such as Li [Li _1/3 Ti _5/3 ] O ₄ , titanium disulfide, or molybdenum disulfide, is used, film formation under a low temperature condition is desired. It is.

  A plurality of units 20 are manufactured, and the plurality of units 20 are stacked so that the plurality of units 20 form an electrical series connection. As shown in FIG. 3, when the second active material layer 12, the solid electrolyte layer 13, and the first active material layer 14 are disposed between the first metal layer 11 and the second metal layer 15, a certain unit 20 The stacking step can be performed such that the second metal layer 15 of another unit 20 (second unit) is in contact with the first metal layer 11 of (first unit). Thereby, the battery 40 is obtained. By increasing the number of units 20, the voltage of the battery 40 can be increased. Similar to the first embodiment, the plurality of units 20 may be joined or connected via a conductive layer having adhesiveness.

(Modification 2)
As shown in FIG. 4, the stacked all solid state battery 40 a is formed by alternately stacking the units 20 and the units 20 a. In the unit 20a, the first metal layer 11, the first active material layer 14, the solid electrolyte layer 13, the second active material layer 12, and the second metal layer 15 are laminated in this order. That is, the arrangement of the second active material layer 12 and the first active material layer 14 between the first metal layer 11 and the second metal layer 15 is not limited. In the unit 20 a, the first active material layer 14 is in contact with the first metal layer 11, and the second active material layer 12 is in contact with the second metal layer 15. This arrangement is opposite to the arrangement of the second active material layer 12 and the first active material layer 14 in the unit 20.

  In the battery 40a, the first metal layers 11 are in contact with each other directly or through a conductive layer, and the second metal layers 15 are in contact with each other directly or through a conductive layer. Of course, it is also possible to obtain a stacked all solid state battery using only the plurality of units 40a.

  As described above, the method disclosed in the present specification not only can reduce manufacturing loss, but also is not easily limited by the type of solid electrolyte. As a result, an all-solid battery having high energy density and high reliability can be provided at low cost.

  The all-solid-state battery manufactured by the method disclosed in the present specification can be widely used in portable devices, hybrid vehicles, plug-in hybrid vehicles, electric vehicles, stationary power supplies, and the like.

10, 10a, 20, 20a Unit 11 First metal layer 12 Second active material layer 13 Solid electrolyte layer 14 First active material layer 15 Second metal layers 30, 30a, 40, 40a Multilayer all solid state battery

Claims (9)

Producing a first unit and a second unit each having a structure in which a solid electrolyte layer and an active material layer are disposed between a pair of metal layers;
Laminating the second unit on the first unit such that the first unit and the second unit form an electrical series connection;
A method for producing a laminated all solid state battery. The pair of metal layers includes a first metal layer and a second metal layer formed by different methods;
The method for manufacturing a stacked all-solid-state battery according to claim 1, wherein the stacking step is performed so that the second metal layer of the second unit is in contact with the first metal layer of the first unit. The pair of metal layers includes a first metal layer and a second metal layer formed by different methods;
3. The step of manufacturing the first unit and the second unit uses a metal foil or a metal thin plate as the first metal layer, and forms the second metal layer by a film forming method. A method for producing a laminated all solid state battery.   4. The method for manufacturing a stacked all-solid battery according to claim 2, wherein a thickness of the second metal layer is smaller than a thickness of the first metal layer. The pair of metal layers includes a first metal layer and a second metal layer formed by different methods;
In the step of manufacturing the first unit and the second unit, the first metal layer is brought into contact with one main surface of the solid electrolyte layer, and the active material layer is brought into contact with the other main surface of the solid electrolyte layer The manufacturing method of the laminated | stacked all-solid-state battery of any one of Claims 1-4. The pair of metal layers includes a first metal layer and a second metal layer formed by different methods;
In the step of manufacturing the first unit and the second unit, a method of forming the solid electrolyte layer, a method of forming the active material layer, and a method of forming the second metal layer are respectively a sputtering method and a vapor deposition method. The manufacturing method of the laminated | stacked all-solid-state battery of any one of Claims 1-5 which is a thermal spray method, a cold spray method, or an aerosol deposition method.   The method for producing a stacked all-solid-state battery according to claim 6, wherein the method for forming the solid electrolyte layer and the method for forming the active material layer are a thermal spray method, a cold spray method, or an aerosol deposition method. When the active material layer is defined as the first active material layer,
In the step of fabricating the first unit and the second unit, the first active material layer has an operating potential different from that of the first active material layer and a polarity opposite to the first active material layer, and the first unit and the second unit are interposed through the solid electrolyte layer The manufacturing method of the laminated | stacked all-solid-state battery of any one of Claims 1-7 which further forms the 2nd active material layer separated from the 1 active material layer. A first unit having a structure in which a solid electrolyte layer and an active material layer are disposed between the first metal layer and the second metal layer;
A second unit that has a structure in which the solid electrolyte layer and the active material layer are disposed between the first metal layer and the second metal layer, and is stacked on the first unit;
With
The thickness of the second metal layer is smaller than the thickness of the first metal layer,
A stacked all solid state battery, wherein the first unit is stacked on the second unit such that the first unit and the second unit form an electrical series connection.

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