JP2014102982A - All-solid-state battery and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an all-solid-state battery capable of simplifying a manufacturing process, and a manufacturing method for the same.SOLUTION: The all-solid-state battery comprises a pair of electrode layers, and a solid electrolyte layer held between the pair of electrode layers, in which an insulation member is disposed at an outer surface edge on the solid electrolyte layer side of the pair of electrode layers or one of the pair of electrode layers, and the solid electrolyte layer is disposed in a region enclosed by the insulation member. The manufacturing method for the all-solid-state battery includes: an insulation member disposition step of disposing the insulation member at the outer surface edge of the electrode layer; an electrolyte formation step of forming the solid electrolyte layer on the surface of a base material; and a transfer step of transferring the solid electrolyte layer to the electrode layers by pressing the solid electrolyte layer formed on the surface of the base material and the insulation member disposed at the outer surface edge of the electrode layer while being contacted with each other.

Description

  The present invention relates to an all-solid battery and a method for manufacturing the same.

  Lithium ion secondary batteries have a higher energy density than conventional secondary batteries and can be operated at a high voltage. For this reason, it is used as a secondary battery that can be easily reduced in size and weight in information equipment such as a mobile phone, and in recent years, there is an increasing demand for large motive power such as for electric vehicles and hybrid vehicles.

  A lithium ion secondary battery has a positive electrode layer and a negative electrode layer, and an electrolyte layer disposed between them. Examples of the electrolyte used for the electrolyte layer include non-aqueous liquid and solid substances. Are known. When a liquid electrolyte (hereinafter referred to as “electrolytic solution”) is used, the electrolytic solution easily penetrates into the positive electrode layer and the negative electrode layer. Therefore, an interface between the active material contained in the positive electrode layer or the negative electrode layer and the electrolytic solution is easily formed, and the performance is easily improved. However, since the widely used electrolyte is flammable, it is necessary to mount a system for ensuring safety. On the other hand, when a solid electrolyte that is flame retardant (hereinafter referred to as “solid electrolyte”) is used, the above system can be simplified. Therefore, development of a lithium ion secondary battery (hereinafter, sometimes referred to as “all-solid battery”) in a form provided with a layer containing a solid electrolyte (hereinafter referred to as “solid electrolyte layer”) proceeds. It has been.

  As a technique relating to such a lithium ion secondary battery, for example, Patent Document 1 discloses a bipolar electrode having a positive electrode layer on one surface of a current collector foil and a negative electrode layer on the other surface. In a bipolar battery having a structure laminated via a polymer electrolyte layer, a technique is disclosed in which an insulating layer is provided on the periphery of at least one surface of a current collector foil. In addition, the drawing of Patent Document 1 shows an insulating layer whose thickness is equal to or less than the thickness of the positive electrode layer or the negative electrode layer, and paragraph 0025 of the specification includes a positive electrode layer on the current collector foil. It is described that it is desirable to use a thin insulating film equivalent to or less than the thickness of the negative electrode layer.

JP 2004-134116 A

  In the technique disclosed in Patent Document 1, after forming a bipolar electrode having an exposed portion (a portion where a positive electrode layer or a negative electrode layer is not formed; the same applies hereinafter) on the outer edge of the current collector foil, the exposed portion is exposed to the exposed portion. A bipolar battery is manufactured through a process of disposing an insulating film. However, this method requires a step of securing the exposed portion and a step of disposing an insulating film in accordance with the exposed portion, so that the battery manufacturing process is likely to be complicated.

  Then, this invention makes it a subject to provide the all-solid-state battery which can simplify a manufacturing process, and its manufacturing method.

  As a result of intensive studies, the inventor has simplified the alignment of the insulating member by manufacturing an all-solid battery through a process in which the insulating member disposed on the outer edge of the electrode layer and the solid electrolyte layer are brought into contact with each other and pressed. However, it was found that the solid electrolyte layer can be transferred to the electrode layer, which facilitates the production of an all-solid battery. The present invention has been completed based on this finding.

In order to solve the above problems, the present invention takes the following means. That is,
A first aspect of the present invention includes a pair of electrode layers and a solid electrolyte layer sandwiched between the pair of electrode layers, and the pair of electrode layers or one of the electrode layers on the outer edge of the surface on the solid electrolyte layer side. An all-solid battery in which an insulating member is disposed and a solid electrolyte layer is disposed in a region surrounded by the insulating member.

Here, in the first aspect of the present invention and other aspects of the present invention (hereinafter, simply referred to as “the present invention”), “a pair of electrode layers” means a positive electrode layer and a negative electrode Refers to the layer. In the present invention, the “insulating member” may be disposed only at the outer surface edge of the positive electrode layer on the solid electrolyte layer side, or may be disposed only at the outer surface edge of the negative electrode layer on the solid electrolyte layer side. The surface outer edge on the solid electrolyte layer side and the surface outer edge on the solid electrolyte layer side of the negative electrode layer may be disposed. Moreover, in this invention, the insulating member should just be arrange | positioned at the surface outer edge of the electrode layer of the solid electrolyte layer side. The side surface of the insulating member may be flush with the side surface of the electrode layer, and the side surface of the insulating member may exist outside the side surface of the electrode layer.
By disposing the insulating member on the outer peripheral surface of the electrode layer on the solid electrolyte layer side, the alignment of the insulating member is facilitated. Moreover, since it is not essential to form the exposed portion on the outer edge of the current collector foil, the manufacturing process can be simplified. Further, such an all-solid battery can be manufactured through a process in which an insulating member disposed on the outer edge of the electrode layer and a solid electrolyte layer are brought into contact with each other and pressed. Therefore, at the time of pressing, it is possible to cause a crack at the boundary between the portion of the solid electrolyte layer that is in contact with the insulating member and the portion of the solid electrolyte layer that is not in contact with the insulating member. By intentionally splitting the solid electrolyte layer by generating cracks, the solid electrolyte layer can be easily arranged in a region surrounded by the insulating member, and the solid electrolyte layer remaining on the surface of the insulating member Some can be easily removed by methods such as giving a light impact or sending wind. Therefore, the all-solid-state battery which can simplify a manufacturing process can be provided by setting it as this form.

  In the first aspect of the present invention, the insulating member is preferably thinner than the solid electrolyte layer. By adopting such a form, it becomes easy to press the solid electrolyte layer, and in addition to the above effects, it becomes easy to obtain an all-solid battery with improved volume energy density.

  In the first aspect of the present invention, the arithmetic average roughness Ra of the surface of the insulating member that contacts the solid electrolyte layer during production is preferably 6.3 μmRa or less. By setting it as this form, since it becomes easy to remove an unnecessary part of a solid electrolyte layer from an insulating member easily, it becomes easier to further simplify a manufacturing process.

  According to a second aspect of the present invention, an all-solid battery including a pair of electrode layers, a solid electrolyte layer sandwiched between the pair of electrode layers, and an insulating member disposed around the solid electrolyte layer is manufactured. An insulating member disposing step for disposing an insulating member on the outer edge of the surface of the electrode layer, an electrolyte forming step for forming a solid electrolyte layer on the surface of the base material, and a solid electrolyte layer formed on the surface of the base material And a transfer step of transferring the solid electrolyte layer to the electrode layer by pressing in a state where the insulating member arranged on the outer edge of the electrode layer is in contact with the electrode layer. .

  By disposing the insulating member on the outer edge of the surface of the electrode layer, alignment of the insulating member is facilitated. Moreover, since it becomes unnecessary to form an exposed part in the outer edge of current collection foil by setting it as this form, it becomes possible to simplify a manufacturing process. In the transfer step, it is possible to cause a crack at the boundary between the portion of the solid electrolyte layer that is in contact with the insulating member and the portion of the solid electrolyte layer that is not in contact with the insulating member. By intentionally splitting the solid electrolyte layer by generating cracks, the solid electrolyte layer can be easily arranged in a region surrounded by the insulating member, and the solid electrolyte layer remaining on the surface of the insulating member A part can be easily removed by a method such as sending wind. Therefore, by setting it as this form, the manufacturing method of an all-solid-state battery which can simplify the manufacturing process of an all-solid-state battery can be provided.

  In the second aspect of the present invention, the insulating member is preferably thinner than the solid electrolyte layer. By adopting such a form, it becomes easy to press the solid electrolyte layer. In addition to the above effects, it becomes easy to manufacture an all-solid battery with an improved volume energy density.

  In the second aspect of the present invention, the arithmetic average roughness Ra of the surface of the insulating member that contacts the solid electrolyte layer in the pressing step is preferably 6.3 μmRa or less. By adopting such a configuration, a part of the solid electrolyte layer (debris) disposed on the surface of the insulating member in the pressing process can be easily removed from the insulating member, so that the manufacturing process can be further simplified. .

  ADVANTAGE OF THE INVENTION According to this invention, the all-solid-state battery which can simplify a manufacturing process, and its manufacturing method can be provided.

It is a flowchart explaining the manufacturing method of an all-solid-state battery. It is a figure explaining the manufacturing method of an all-solid-state battery. 1 is a diagram illustrating an all solid state battery 10. FIG. It is a figure explaining a transfer process. It is a figure which shows the mode immediately after the transcription | transfer process. It is a figure which shows the mode after debris removal.

  The present invention will be described below with reference to the drawings. In the following description, for convenience, the same reference numerals are given to the layer before pressing and the layer after pressing. In addition, the form shown below is an illustration of this invention and this invention is not limited to the form shown below.

  FIG. 1 is a flowchart for explaining a method for producing an all solid state battery of the present invention, and FIG. 2 is a cross-sectional view for explaining a method for producing the all solid state battery of the present invention shown in FIG. With reference to FIG. 1 and FIG. 2, a method for producing an all solid state battery of the present invention (hereinafter sometimes referred to as “manufacturing method of the present invention”) will be described below.

  The manufacturing method of the present invention shown in FIG. 1 includes an electrode layer preparation step (S1), an insulating member placement step (S2), an electrolyte formation step (S3), a transfer step (S4), and an electrode body formation step ( S5).

  The electrode layer manufacturing step (hereinafter sometimes referred to as “S1”) is a step of manufacturing a pair of electrode layers. The form of S1 is not particularly limited as long as a pair of electrode layers can be formed, and a known method can be appropriately used. For example, as shown in FIG. 2, S <b> 1 can be a step of producing the positive electrode layer 1 on the surface of the positive electrode current collector 4 and producing the negative electrode layer 2 on the surface of the negative electrode current collector 5. In S <b> 1, the positive electrode layer 1 can be produced, for example, through a process in which a slurry-like positive electrode composition containing a positive electrode active material and a solid electrolyte is applied to the surface of the positive electrode current collector 4 and dried. The negative electrode layer 2 can be produced, for example, through a process in which a slurry-like negative electrode composition containing a negative electrode active material and a solid electrolyte is applied to the surface of the negative electrode current collector 5 and dried. In S <b> 1, the positive electrode layer 1 can be produced on the entire upper surface of the positive electrode current collector 4, and the negative electrode layer 2 can be produced on the entire upper surface of the negative electrode current collector 5. That is, in S1, since it is not essential to secure an exposed portion where the positive electrode layer 1 or the negative electrode layer 2 is not disposed on the outer edge of the positive electrode current collector 4 or the negative electrode current collector 5, it is necessary to ensure the exposed portion. Compared with the prior art, the electrode layer can be easily manufactured.

  The insulating member disposing step (hereinafter sometimes referred to as “S2”) is a step of disposing the insulating member on the outer edge of the surface of the electrode layer fabricated in S1. S2 can be, for example, a step of disposing a frame-shaped insulating member 6 having an opening at the center on the outer edge of the upper surface side surface of the positive electrode layer 1 produced on the surface of the positive electrode current collector 4. . In S2, since the insulating member may be disposed on the outer edge of the surface of the electrode layer produced in S1, the insulating member is compared with the conventional technique in which the insulating member is disposed in the exposed portion secured around the electrode layer. It can be easily arranged. In addition, S2 can also be set as the process of arrange | positioning the insulating member which has an opening part in the center to the outer edge of the upper surface side surface of the negative electrode layer 2 produced in the surface of the negative electrode collector 5. FIG. In addition, it is also possible to set the insulating member having an opening in the center to the outer edges of the upper surface side surfaces of the positive electrode layer 1 and the negative electrode layer 2.

  The electrolyte forming step (hereinafter, sometimes referred to as “S3”) is a step of forming the solid electrolyte layer 3 on the surface of the substrate 8. If S3 can form the solid electrolyte layer 3, the form will not be specifically limited, A well-known method can be used suitably. For example, S3 can be a step of forming the solid electrolyte layer 3 through a process of applying a slurry-like solid electrolyte composition containing a solid electrolyte and a binder to the surface of the substrate 8 and drying it.

  In the transfer step (hereinafter sometimes referred to as “S4”), the solid electrolyte layer formed on the surface of the substrate in S3 and the insulating member disposed on the outer edge of the electrode layer in S2 were brought into contact with each other. This is a step of transferring the solid electrolyte layer from the substrate to the electrode layer by pressing in a state. In S4, for example, the solid electrolyte layer 3 formed on the surface of the substrate 8 and the insulating member 6 disposed on the outer surface edge of the upper surface of the positive electrode layer 1 are covered with the solid electrolyte layer 3 at the opening of the insulating member 6. By pressing in a state of being in contact with the insulating member 6, the portion of the solid electrolyte layer 3 (solid electrolyte layer 3 ′) facing the opening of the insulating member 6 can be transferred to the positive electrode layer 1. .

  As shown in FIG. 2, the insulating member 6 has an opening at the center. Therefore, when the solid electrolyte layer 3 is disposed so as to cover the opening of the insulating member 6 in S4, the solid electrolyte layer 3 has a portion that is in contact with the insulating member 6 and a portion that is not in contact with the insulating member 6 (solid It can be divided into electrolyte layers 3 ′). When pressed in a state where the insulating member 6 and the solid electrolyte layer 3 are in contact with each other, the portion of the solid electrolyte layer 3 that is in contact with the insulating member 6 and the portion of the solid electrolyte layer 3 that is not in contact with the insulating member 6 (solid It is possible to cause a crack at the boundary with the electrolyte layer 3 ′). Then, by pressing until the generated crack has propagated over the entire length in the thickness direction of the solid electrolyte layer 3, the portion of the solid electrolyte layer 3 facing the opening of the insulating member 6 (solid electrolyte layer 3 ′) ) Can be dropped into a region surrounded by the insulating member 6, thereby bringing the solid electrolyte layer 3 ′ that has fallen into the region surrounded by the insulating member 6 into contact with the positive electrode layer 1 (solid electrolyte layer). Can be transferred from the substrate 8 to the positive electrode layer 1).

  When the solid electrolyte layer 3 ′ is dropped in a region surrounded by the insulating member 6, a part (debris) of the solid electrolyte layer 3 can be disposed on the upper surface of the insulating member 6. Debris of the solid electrolyte layer 3 disposed on the upper surface of the insulating member 6 can be easily removed by applying a light impact or supplying air to the upper surface of the insulating member 6 with a blower or the like. It is.

  The electrode body forming step (hereinafter sometimes referred to as “S5”) is sandwiched between a pair of electrode layers by disposing another electrode layer on the surface of the solid electrolyte layer transferred to the electrode layer in S4. In this step, an electrode body including the solid electrolyte layer is formed. S5 is, for example, through a process of laminating the solid electrolyte layer 3 ′ brought into contact with the positive electrode layer 1 in S4 and the negative electrode layer 2 produced on the surface of the negative electrode current collector 5 in S1. The step of forming the electrode body 7 including the solid electrolyte layer 3 sandwiched between the positive electrode layer 1 and the negative electrode layer 2 can be used. After forming the electrode body 7 in this manner, for example, after pressing at a predetermined pressure, the pressed electrode body is accommodated in an exterior body and sealed to manufacture an all-solid-state battery. Can do.

As described above, according to the manufacturing method of the present invention, in particular, by disposing an insulating member on the outer edge of the surface of the electrode layer and pressing the insulating member and the solid electrolyte layer in contact with each other. It is possible to simplify the manufacturing process of the all solid state battery as compared with the conventional case.
In addition, in the said description, although the form in which an electrolyte formation process is performed after an electrode layer preparation process and an insulating member arrangement | positioning process was illustrated, this invention is not limited to the said form. In the present invention, for example, the electrolyte forming step can be performed before the electrode layer manufacturing step and the insulating member arranging step.

  FIG. 3 is a cross-sectional view illustrating the all solid state battery 10 that can be manufactured by the manufacturing method of the present invention. In FIG. 3, the description of the exterior body etc. that wraps the electrode body 7 is omitted, and the same reference numerals as those used in FIG. 2 are given to the layers made of the same material as the layers shown in FIG. 2. ing.

  The all solid state battery 10 shown in FIG. 3 includes a positive electrode current collector 4, a positive electrode layer 1 connected to the positive electrode current collector 4, and a positive electrode layer 1 opposite to the positive electrode current collector 4. The insulating member 6 disposed, the solid electrolyte layer 3 ′ disposed in the region surrounded by the insulating member 6, the negative electrode layer 2 disposed so as to sandwich the solid electrolyte layer 3 ′ together with the positive electrode layer 1, An electrode body 7 including a negative electrode current collector 5 connected to the negative electrode layer 2. In the all solid state battery 10, the solid electrolyte layer 3 ′ is sandwiched between a pair of electrode layers (the positive electrode layer 1 and the negative electrode layer 2).

  The all solid state battery 10 configured as described above can be manufactured by the manufacturing method of the present invention. In the all-solid-state battery 10, since the insulating member 6 is disposed on the outer edge of the positive electrode layer 1, it is possible to prevent a short circuit at the outer edge of the positive electrode layer 1 or the negative electrode layer 2. In addition, as described above, according to the manufacturing method of the present invention, the manufacturing process of the all-solid-state battery can be simplified as compared with the conventional method. Therefore, according to the present invention, the manufacturing process can be simplified as compared with the conventional method. Can be provided.

  In the present invention, the thickness of the insulating member 6 (the thickness in the vertical direction of the paper in FIGS. 2 and 3; the same applies hereinafter) is not particularly limited. However, the thickness of the insulating member 6 is larger than the thickness of the solid electrolyte layer 3 from the viewpoint of making it easy to obtain the all solid state battery 10 whose volume energy density is improved by sufficiently pressing the solid electrolyte layer 3 ′. Thin is preferred. Further, from the viewpoint of making the solid electrolyte layer 3 ′ easily disposed in the region surrounded by the insulating member 6, when the thickness of the insulating member 6 is T and the thickness of the solid electrolyte layer 3 is A, It is preferable that T ≧ A / 2.

  Moreover, in this invention, the surface roughness of the surface of the insulating member 6 which contacts the solid electrolyte layer 3 at the time of manufacture (in a press process) is not specifically limited. However, it is preferable that the arithmetic average roughness Ra is 6.3 μmRa or less from the viewpoint of making it possible to easily remove the debris of the solid electrolyte layer disposed on the upper surface of the insulating member 6. As will be described later, when the solid electrolyte contained in the solid electrolyte layer 3 is in the form of particles, the average particle diameter (D50; the same applies hereinafter) can be 0.1 μm or more, and 0.5 μm or more. It is preferable to do. The average particle size of the solid electrolyte that is in the form of particles can be 100 μm or less, preferably 20 μm or less, and more preferably 10 μm or less. In the present invention, the solid electrolyte layer 3 brought into contact with the insulating member 6 in the pressing step can be in a state before being pressed (a state where it is not pressed), and the solid electrolyte layer 3 and the insulating member before being pressed. When contacting 6, some particles contained in the solid electrolyte layer 3 may be disposed on the surface of the insulating member 6. Even if a part of the solid electrolyte layer 3 remains arranged on the surface of the insulating member 6 in this manner, there is a low possibility of adverse effects when operating the all solid state battery. However, since the solid electrolyte disposed on the surface of the insulating member 6 (solid electrolyte sandwiched between the positive electrode layer 1 and the negative electrode layer 2 together with the insulating member 6) is considered not to contribute to ionic conduction, the volume energy density is easily improved. It is preferable to remove this before performing an electrode body formation process from a viewpoint of making it into a form. Therefore, based on the average particle diameter of the particulate solid electrolyte that can be included in the solid electrolyte layer 3, the arithmetic average roughness Ra of the insulating member 6 is 6 from the viewpoint of making the solid electrolyte difficult to remain on the surface of the insulating member 6. It is preferable to be 3 μmRa or less. More preferably, it is 1.0 μmRa or less.

  Further, in the present invention, the hardness of the insulating member 6 is not particularly limited, but from the viewpoint of easily arranging the solid electrolyte layer 3 ′ in a region surrounded by the insulating member 6, It is preferably harder than the hardness.

In the present invention, as the positive electrode active material contained in the positive electrode layer 1, a positive electrode active material that can be used in an all-solid battery can be appropriately used. As such a positive electrode active material, in addition to a layered active material such as lithium cobaltate (LiCoO ₂ ) and lithium nickelate (LiNiO ₂ ), an olivine type active material such as olivine type lithium iron phosphate (LiFePO ₄ ), A spinel type active material such as spinel type lithium manganate (LiMn ₂ O ₄ ) can be exemplified. The shape of the positive electrode active material can be, for example, particulate or thin film. The average particle diameter of the positive electrode active material is preferably, for example, from 1 nm to 100 μm, and more preferably from 10 nm to 30 μm. Further, the content of the positive electrode active material in the positive electrode layer 1 is not particularly limited, but is preferably 40% or more and 99% or less in mass%, for example.

In the present invention, not only the solid electrolyte layer 3 but also the positive electrode layer 1 and the negative electrode layer 2 can contain a known solid electrolyte that can be used for an all-solid battery, if necessary. Examples of such solid electrolytes include oxide-based amorphous solid electrolytes such as Li ₂ O—B ₂ O ₃ —P ₂ O ₅ and Li ₂ O—SiO ₂ , Li ₂ S—SiS ₂ , LiI—Li _{2. S-SiS 2, LiI-Li} 2 S-P 2 S 5, LiI-Li 2 S-P 2 O 5, LiI-Li 3 PO 4 -P 2 S 5, Li 2 S-P 2 S 5, Li 3 in addition to the sulfide-based amorphous solid electrolyte of PS _{4, etc., LiI, Li 3 N, Li} 5 La 3 Ta 2 O 12, Li 7 La 3 Zr 2 O 12, Li 6 BaLa 2 Ta 2 O 12, Li 3 Examples thereof include crystalline oxides and oxynitrides such as PO _{(4-3 / 2w)} N _w (w is w <1) and Li _3.6 Si _0.6 P _0.4 O ₄ . However, it is preferable to use a sulfide solid electrolyte as the solid electrolyte from the viewpoint of making the electrode layer in a form that can easily improve the performance of the all-solid battery.

When a sulfide solid electrolyte is used as the solid electrolyte, the positive electrode active material is formed from the viewpoint of making it easy to prevent an increase in battery resistance by making it difficult to form a high resistance layer at the interface between the positive electrode active material and the solid electrolyte. It is preferable that it is coated with an ion conductive oxide. Examples of the lithium ion conductive oxide that coats the positive electrode active material include a general formula Li _x AO _y (A is B, C, Al, Si, P, S, Ti, Zr, Nb, Mo, Ta, or W). And x and y are positive numbers). Specifically, Li ₃ BO ₃ , LiBO ₂ , Li ₂ CO ₃ , LiAlO ₂ , Li ₄ SiO ₄ , Li ₂ SiO ₃ , Li ₃ PO ₄ , Li ₂ SO ₄ , Li ₂ TiO ₃ , Li ₄ Ti ₅ Examples include O ₁₂ , Li ₂ Ti ₂ O ₅ , Li ₂ ZrO ₃ , LiNbO ₃ , Li ₂ MoO ₄ , Li ₂ WO _{4 and the} like. The lithium ion conductive oxide may be a complex oxide. As the composite oxide covering the positive electrode active material, any combination of the above lithium ion conductive oxides can be employed. For example, Li ₄ SiO ₄ —Li ₃ BO ₃ , Li ₄ SiO ₄ —Li ₃ PO ₄ etc. can be mentioned. Further, when the surface of the positive electrode active material is coated with an ion conductive oxide, the ion conductive oxide only needs to cover at least a part of the positive electrode active material, and covers the entire surface of the positive electrode active material. Also good. In addition, the thickness of the ion conductive oxide covering the positive electrode active material is, for example, preferably from 0.1 nm to 100 nm, and more preferably from 1 nm to 20 nm. The thickness of the ion conductive oxide can be measured using, for example, a transmission electron microscope (TEM).

  Moreover, the positive electrode layer 1 can be produced using a known binder that can be contained in the positive electrode layer of an all-solid battery. Examples of such a binder include acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), polyvinylidene fluoride (PVdF), styrene butadiene rubber (SBR), and the like.

  Furthermore, the positive electrode layer 1 may contain a conductive material that improves conductivity. Examples of the conductive material that can be contained in the positive electrode layer 1 include carbon materials such as vapor grown carbon fiber, acetylene black (AB), ketjen black (KB), carbon nanotube (CNT), and carbon nanofiber (CNF). In addition, a metal material that can withstand the environment during use of the all-solid-state battery can be exemplified. When the positive electrode layer 1 is produced using the positive electrode active material, the solid electrolyte, the slurry-like positive electrode composition prepared by dispersing the binder in the liquid, heptane or the like may be exemplified as a usable liquid. A nonpolar solvent can be preferably used. Moreover, the thickness of the positive electrode layer 1 is, for example, preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less. Moreover, in order to make it easy to improve the performance of the all-solid-state battery 10, the positive electrode layer 1 is preferably manufactured through a pressing process. In this invention, the pressure at the time of pressing the positive electrode layer 1 can be about 400 MPa.

Moreover, as a negative electrode active material contained in the negative electrode layer 2, the well-known negative electrode active material which can occlude-release lithium ion can be used suitably. Examples of such a negative electrode active material include a carbon active material, an oxide active material, and a metal active material. The carbon active material is not particularly limited as long as it contains carbon, and examples thereof include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon. Examples of the oxide active material include Nb ₂ O ₅ , Li ₄ Ti ₅ O ₁₂ , and SiO. Examples of the metal active material include In, Al, Si, and Sn. Further, a lithium-containing metal active material may be used as the negative electrode active material. The lithium-containing metal active material is not particularly limited as long as it is an active material containing at least Li, and may be Li metal or Li alloy. Examples of the Li alloy include an alloy containing Li and at least one of In, Al, Si, and Sn. The shape of the negative electrode active material can be, for example, particulate or thin film. The average particle size of the negative electrode active material is, for example, preferably from 1 nm to 100 μm, and more preferably from 10 nm to 30 μm. Further, the content of the negative electrode active material in the negative electrode layer 2 is not particularly limited, but is preferably in a range of 40% to 99% by mass%, for example.

  Furthermore, the negative electrode layer 2 may contain a binder that binds the negative electrode active material and the solid electrolyte and a conductive material that improves conductivity. Examples of the binder and conductive material that can be contained in the negative electrode layer 2 include the binder and conductive material that can be contained in the positive electrode layer 1. Moreover, when producing the negative electrode layer 2 using the slurry-like negative electrode composition prepared by dispersing the negative electrode active material or the like in a liquid, heptane or the like may be exemplified as the liquid in which the negative electrode active material or the like is dispersed. A nonpolar solvent can be preferably used. Further, the thickness of the negative electrode layer 2 is, for example, preferably from 0.1 μm to 1 mm, and more preferably from 1 μm to 100 μm. Moreover, in order to make it easy to improve the performance of the all-solid-state battery 10, the negative electrode layer 2 is preferably manufactured through a pressing process. In the present invention, the pressure when pressing the negative electrode layer 2 is preferably 200 MPa or more, more preferably about 400 MPa.

  Moreover, as a solid electrolyte contained in the solid electrolyte layer 3, a known solid electrolyte that can be used in an all-solid battery can be appropriately used. Examples of such a solid electrolyte include the solid electrolyte that can be contained in the positive electrode layer 1 and the negative electrode layer 2. In addition, the solid electrolyte layer 3 can contain a binder that binds the solid electrolytes from the viewpoint of developing plasticity. As such a binder, the said binder etc. which can be contained in the positive electrode layer 1 can be illustrated. However, in order to facilitate high output, the solid electrolyte layer 3 can be formed from the viewpoint of preventing excessive aggregation of the solid electrolyte and enabling the formation of the solid electrolyte layer 3 having a uniformly dispersed solid electrolyte. The binder to be contained is preferably 5% by mass or less. Further, when the solid electrolyte layer 3 is produced through a process of applying the slurry-like solid electrolyte composition prepared by dispersing the solid electrolyte or the like in the liquid to the base 8 or the like, the liquid for dispersing the solid electrolyte or the like , Heptane and the like, and a nonpolar solvent can be preferably used. The content of the solid electrolyte material in the solid electrolyte layer 3 is mass%, for example, preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. The thickness of the solid electrolyte layer 3 varies greatly depending on the configuration of the battery. For example, the thickness is preferably 0.1 μm or more and 1 mm or less, and more preferably 1 μm or more and 100 μm or less. Moreover, the solid electrolyte contained in the solid electrolyte layer 3 can be made into a particulate form, for example. When the solid electrolyte layer 3 contains a particulate solid electrolyte, the average particle diameter of the solid electrolyte can be 0.1 μm or more, preferably 0.5 μm or more. The average particle size of the solid electrolyte that is in the form of particles can be 100 μm or less, preferably 20 μm or less, and more preferably 10 μm or less.

  The positive electrode current collector 4 and the negative electrode current collector 5 can be made of a known conductive material that can be used as a current collector of an all-solid battery. Examples of such a conductive material include one or more elements selected from the group consisting of Cu, Ni, Al, V, Au, Pt, Mg, Fe, Ti, Co, Cr, Zn, Ge, and In. Examples of the metal material to be included can be given.

  Moreover, the insulating member 6 arrange | positioned at the surface outer edge of the positive electrode layer 1 and / or the negative electrode layer 2 can use suitably the well-known insulating material which can endure the use environment of an all-solid-state battery. As such an insulating material, a known insulating film (insulating flexible film) or the like can be used. The surface of the insulating member used in the present invention that does not contact the solid electrolyte layer (for example, the surface that contacts the electrode layer) may have adhesiveness. Specific examples of the insulating member 6 include a polyimide film, a polyimide adhesive film, a polyester film, a polyester adhesive film, a polyolefin film, a polyolefin adhesive film, a polytetrafluoroethylene film, and a polytetrafluoroethylene adhesive film.

  Moreover, as the exterior body that wraps the electrode body 7, a known exterior body that can be used in an all-solid-state battery can be appropriately used. Examples of such an exterior body include a resin laminate film, a film obtained by vapor-depositing a metal on a resin laminate film, and the like.

  In the said description regarding this invention, although the all-solid-state battery illustrated the form which is a lithium ion secondary battery, this invention is not limited to the said form. The all-solid-state battery and the manufacturing method thereof of the present invention can also be applied to a form in which ions other than lithium ions move between the positive electrode layer and the negative electrode layer. Examples of such ions include sodium ions and potassium ions. In the case where ions other than lithium ions move, the positive electrode active material, the solid electrolyte, and the negative electrode active material may be appropriately selected according to the moving ions.

A negative electrode layer was formed on the surface of the current collector foil through a process of applying a slurry-like negative electrode composition containing a negative electrode active material and a solid electrolyte to the surface of the current collector foil (copper foil, negative electrode current collector). Thereafter, the current collector foil on which the negative electrode layer was formed was placed on a table. Then, a polyimide adhesive tape (thickness 60 μm, surface arithmetic average roughness Ra <2.0 μm) is applied across the upper surface outer edge of the negative electrode layer, the negative electrode layer and the side surface of the current collector foil, and the base, whereby the negative electrode layer In addition, an insulating member was disposed on the outer edge of the upper surface, and the current collector foil on which the negative electrode layer was formed was fixed on a table.
On the other hand, a slurry electrolyte composition containing a solid electrolyte and a binder was applied to the surface of the base material (aluminum foil) and dried to form a solid electrolyte layer having a thickness of 30 μm on the surface of the base material. Subsequently, these were laminated | stacked so that the insulating member arrange | positioned at the outer periphery of the upper surface of a negative electrode layer and the solid electrolyte layer formed on the base material might be contacted, and it pressed by the pressure of 98 Mpa after that. FIG. 4 shows a conceptual diagram immediately before and after pressing the insulating member and the solid electrolyte layer. Further, FIG. 5 shows an actual photograph immediately after pressing, and FIG. 6 shows an actual photograph after removing the solid electrolyte on the surface of the insulating member.

As shown in FIGS. 5 and 6, the solid electrolyte layer could be transferred to the negative electrode layer by pressing. Further, as shown in FIG. 5, fragments of the solid electrolyte layer were arranged on a part of the surface of the insulating member arranged at the outer edge of the surface of the negative electrode layer. Then, in order to remove the fragments of the solid electrolyte layer arranged on a part of the surface of the insulating member, air was sent with a blower. Then, as shown in FIG. 6, debris of the solid electrolyte layer could be removed.
As mentioned above, according to this invention, it was confirmed that the manufacturing process of an all-solid-state battery can be simplified.

1 ... Positive electrode layer (electrode layer)
2 ... Negative electrode layer (electrode layer)
DESCRIPTION OF SYMBOLS 3, 3 '... Solid electrolyte layer 4 ... Positive electrode collector 5 ... Negative electrode collector 6 ... Insulating member 7 ... Electrode body 8 ... Base material 10 ... All-solid-state battery

Claims (6)

A pair of electrode layers, and a solid electrolyte layer sandwiched between the pair of electrode layers,
An insulating member is disposed on the surface outer edge of the pair of electrode layers or one of the electrode layers on the solid electrolyte layer side,
An all-solid battery, wherein the solid electrolyte layer is disposed in a region surrounded by the insulating member. The all-solid-state battery according to claim 1, wherein a thickness of the insulating member is thinner than a thickness of the solid electrolyte layer. The all-solid-state battery of Claim 1 or 2 whose arithmetic mean roughness Ra of the surface of the said insulating member which contacts a solid electrolyte layer at the time of manufacture is 6.3 micrometers Ra or less. A method of manufacturing an all-solid battery comprising a pair of electrode layers, a solid electrolyte layer sandwiched between the pair of electrode layers, and an insulating member disposed around the solid electrolyte layer,
An insulating member disposing step of disposing an insulating member on a surface outer edge of the electrode layer;
An electrolyte forming step of forming a solid electrolyte layer on the surface of the substrate;
The solid electrolyte layer is pressed onto the electrode layer by pressing the solid electrolyte layer formed on the surface of the base material and the insulating member disposed on the outer edge of the electrode layer in contact with each other. A transfer process for transferring;
A method for producing an all-solid-state battery. The manufacturing method of the all-solid-state battery according to claim 4, wherein the thickness of the insulating member is thinner than the thickness of the solid electrolyte layer. The method for producing an all-solid-state battery according to claim 4 or 5, wherein an arithmetic mean roughness Ra of a surface of the insulating member that contacts the solid electrolyte layer in the pressing step is 6.3 µmRa or less.